Chromium free hardfacing materials

ABSTRACT

Disclosed are embodiments of Fe-based alloys for use as a hardfacing material having high hardness while avoiding the use of chromium. The alloys can be twin arc or thermally sprayed as coatings on different types of equipment. In some embodiments, the alloys can be readable even after heating of the alloys.

INCORPORATION BY REFERENCE TO ANY PRIORITY APPLICATIONS

Any and all applications for which a foreign or domestic priority claimis identified in the Application Data Sheet as filed with the presentapplication are hereby incorporated by reference under 37 CFR 1.57.

BACKGROUND

1. Field

The disclosure generally relates to hardfacing materials which can bedeposited as hardfacing coatings without the production of Cr, such ashexavalent Cr dust.

2. Description of the Related Art

Thermal spray processing is a technique which can be utilized to deposita hard wear resistant and/or corrosion resistant layer onto the surfaceof a component. Thermal spray inherently creates a significant amount ofdust due to the fact that about 10-40% or more of the feedstock materialdoes not stick to the component of interest and rebounds of the surfacein the form a fine metallic dust. One particular class of thermal spraymaterials which is used to form wear resistant layers is amorphousand/or nanocrystalline materials. Fe-based amorphous and nanocrystallinematerials used in thermal spray contain chromium as an alloying element.Chromium is effective in stabilizing the fine-grained structure, canincrease wear resistance through the formation of chromium carbidesand/or borides, and is useful in providing a degree of corrosionresistance. However, chromium is considered undesirable for use inthermal spray applications due to the potential to form hexavalentchromium dust. Hexavalent chromium dust is known to cause cancer.

There are several Fe-based chromium free thermal spray materials whichhave been developed and are used by industry today. Currently availableFe-based Cr-free materials have hardness levels below 500 Vickers, asshown in Table 1, which can make them inapplicable for many differentindustrial uses.

TABLE 1 Conventional Fe-based Cr-free materials and reported hardnessvalues Alloy Hardness 30T 97-100 FMB (~250 Vickers) 38T 23 HRC (~250Vickers) 39T 34-47 HRC (~330-470 Vickers) 35 MXC 30-35 HRC (~290-330Vickers)

There have also been efforts to specifically design Cr-free hardfacingmaterials for welding processes, such as that shown in 2012/0097658.However, the alloys disclosed in the reference require the formation ofborides and carbides. Further, the reference requires the use of boron.

SUMMARY

Disclosed herein are embodiments of alloy compositions used to producethermal spray coatings, methods of identifying these compositions, thecoatings themselves, and methods of making and using the coatings.Thermal spray coatings according to certain embodiments may be producedhaving a hardness above 500 Vickers without the use of chromium as analloying element. Some embodiments are directed to a work piece having acoating on at least a surface, the work piece comprising a metal surfaceonto which a coating is applied, the coating comprising an Fe-basedalloy without any chromium, wherein the alloy comprises a Vickershardness of at least 500 and an adhesion strength of at least 5,000 psi.

In some embodiments, the coating can be applied via the twin wire arcspray process.

In some embodiments, the coating can comprise, in weight percent, B:about 0-4, C: about 0-0.25, Si: about 0-15, Mn: about 0 to 25, Mo: about0-29, Nb: about 0-2, Ta: about 0-4, Ti: about 0-4, V: about 0-10, W:about 0-6, Zr: about 0-10, wherein B+C+Si is about 4-15, and wherein(Mo+Mn+Nb+Ta+Ti+V+W+Zr) is about 5 to 38.

In some embodiments, the coating can comprise Fe and, in weight percent,C: about 0 to 0.25, Mn: about 5 to 19, Mo: about 7 to 23, Ni: about 0 to4, and Si: about 5 to 10.

In some embodiments, the coating can be non-magnetic and therefore thecoating thickness can be accurately measured with an Elcometer™thickness gauge or similar device. In some embodiments, the coating canbe non-magnetic and therefore the coating thickness can be accuratelymeasured with an Elcometer™ thickness gauge or similar device after ithas been exposed to temperatures exceeding about 1100 K for 2 hours ormore and then slow cooled at a rate of 10K/s or less.

In some embodiments, the coating can be amorphous. In some embodiments,the coating can be nanocrystalline, as defined by having a grain size of100 nm or less.

Also disclosed herein are embodiments of an article of manufacturecomprising a coating which is Fe-based, without chromium, and possessesa melting temperature of 1500K or below and a large atom concentrationof at least 5 atom %, large atoms being of the group Mn, Mo, Nb, Ta, Ti,V, W, and Zr.

In some embodiments, the coating can comprise a Vickers hardness of atleast 400 and an adhesion strength of at least 5,000 psi. In someembodiments, the coating can be applied via the twin wire arc sprayprocess.

In some embodiments, the coating can comprise, in weight percent, B:about 0-4, C: about 0-0.25, Si: about 0-15, Mn: about 0 to 25, Mo: about0-29, Nb: about 0-2, Ta: about 0-4, Ti: about 0-4, V: about 0-10, W:about 0-6, Zr: about 0-10, wherein B+C+Si is about 4-15, and wherein(Mo+Mn+Nb+Ta+Ti+V+W+Zr) is about 5 to 38.

In some embodiments, the coating can comprise Fe and, in weight percent,C: about 0 to 0.25, Mn: about 5 to 19, Mo: about 7 to 23, Ni: about 0 to4, and Si: about 5 to 10.

In some embodiments, the coating can be non-magnetic and therefore thecoating thickness can be accurately measured with an Elcometer™thickness gauge or similar device. In some embodiments, the coating canbe non-magnetic and therefore the coating thickness can be accuratelymeasured with an Elcometer™ thickness gauge or similar device after ithas been exposed to temperatures exceeding about 1100 K for 2 hours ormore and then slow cooled at a rate of 10K/s or less.

In some embodiments, the coating can be amorphous. In some embodiments,the coating can be nanocrystalline, as defined by having a grain size of100 nm or less.

Disclosed herein are embodiments of a work piece having at least onesurface, the work piece comprising a coating applied to the at least onesurface, the coating comprising an Fe-based alloy having substantiallyno chromium, having substantially no carbides, and having substantiallyno borides, wherein the alloy comprises a Vickers hardness of at least500 and an adhesion strength of at least 5,000 psi.

In some embodiments, the coating can comprise Fe and, in weight percent,B: about 0-4, C: about 0-0.25, Si: about 0-15, Mn: about 0 to 25, Mo:about 0-29, Nb: about 0-2, Ta: about 0-4, Ti: about 0-4, V: about 0-10,W: about 0-6, Zr: about 0-10, wherein B+C+Si is about 4-15, and wherein(Mo+Mn+Nb+Ta+Ti+V+W+Zr) is about 5 to 38. In some embodiments, thecoating can comprise Fe and in weight percent, C: about 0 to 0.25, Mn:about 5 to 19, Mo: about 7 to 23, Ni: about 0 to 4, and Si: about 5 to10. In some embodiments, the coating can comprise one or more of thefollowing compositions in weight percent: Fe, Mn: about 5, Mo: about 13,Si: about 10, Al: about 2; or Fe, Mn: about 5, Mo: about 7, Si: about10, Al: about 2.

In some embodiments, the coating can be non-magnetic and the coatingthickness can be accurately measured with an Elcometer™ thickness gaugeor similar device after it has been exposed to temperatures exceedingabout 1100 K for 2 hours or more and then slow cooled at a rate of 10K/sor less.

In some embodiments, the coating can be amorphous. In some embodiments,the coating can be nanocrystalline, as defined by having a grain size of100 nm or less.

In some embodiments, the coating can be applied via a thermal sprayprocess. In some embodiments, the coating can be applied via a twin wirearc spray process. In some embodiments, the work piece can be a yankeedryer. In some embodiments, the work piece can be a roller used in apaper making machine.

Also disclosed herein are embodiments of an article of manufacturecomprising an Fe-based coating having substantially no chromium, whereinthe coating possesses a melting temperature of 1500K or below, whereinthe coating possesses a large atom concentration of at least 5 atom %,large atoms being of the group consisting of Mn, Mo, Nb, Ta, Ti, V, W,and Zr, and wherein the coating is a primarily single phase fine-grainedstructure of either martensite, ferrite, or austenite.

In some embodiments, the coating can comprise, in weight percent B:about 0-4, C: about 0-0.25, Si: about 0-15, Mn: about 0 to 25, Mo: about0-29, Nb: about 0-2, Ta: about 0-4, Ti: about 0-4, V: about 0-10, W:about 0-6, Zr: about 0-10, wherein B+C+Si is about 4-15, and wherein(Mo+Mn+Nb+Ta+Ti+V+W+Zr) is about 5 to 38.

In some embodiments, the coating can comprise Fe and in weight percentC: about 0 to 0.25, Mn: about 5 to 19, Mo: about 7 to 23, Ni: about 0 to4, and Si: about 5 to 10.

In some embodiments, the coating can comprise one or more of thefollowing compositions in weight percent: Fe, Mn: about 5, Mo: about 13,Si: about 10, Al: about 2; or Fe, Mn: about 5, Mo: about 7, Si: about10, Al: about 2.

In some embodiments, the coating can be non-magnetic and the coatingthickness can be accurately measured with an Elcometer™ thickness gaugeor similar device after it has been exposed to temperatures exceedingabout 1100 K for 2 hours or more and then slow cooled at a rate of 10K/sor less. In some embodiments, the coating can comprise a Vickershardness of at least 500 and an adhesion strength of at least 5,000 psi.

In some embodiments, the coating can be applied via the twin wire arcspray process. In some embodiments, the coating can be applied via athermal spray process.

In some embodiments, the coating can be amorphous. In some embodiments,the coating can be nanocrystalline, as defined by having a grain size of100 nm or less.

In some embodiments, the coating can be applied onto a roller used in apaper making machine. In some embodiments, the coating can be appliedonto a Yankee Dryer. In some embodiments, the coating can be appliedonto a boiler tube.

Also disclosed herein are embodiments of a work piece having at leastone surface, the work piece comprising a coating applied to the at leastone surface, the coating comprising an Fe-based alloy having less than 1wt. % chromium, less than 5 vol. % carbides, and less than 5 vol. %borides, wherein the alloy comprises a Vickers hardness of at least 500and an adhesion strength of at least 5,000 psi. In some embodiments, thealloy can have less than 1 vol. % carbides and less than 1 vol. %borides.

DETAILED DESCRIPTION

Disclosed herein are embodiments of chromium free, iron based alloys,and methods of manufacturing the alloys. In some embodiments, the alloyscan have high hardness and can be used as, for example, coatings. Insome embodiments, computational metallurgy can be used to explore alloycompositional ranges where an alloy is likely to form an amorphous ornanocrystalline coating without the use of chromium as an alloyingelement. Prior to this disclosure, Fe-based thermal spray coatings witha hardness above 500 Vickers have used chromium as an alloying element.This disclosure demonstrates embodiments of alloy compositions which canproduce thermal spray coatings with hardness values above 500 Vickers,in addition to describing the design techniques successfully used toidentify them.

Specifically, disclosed herein are embodiments of alloys which canachieve high hardness levels through mechanisms other than the use ofchromium or the formation of carbides and/or borides. Rather, in someembodiments, a very fine-grain structure can be achieved due to meltingtemperature and large atom criteria disclosed herein.

Metal Alloy Composition

In some embodiments, the alloy can be described by a composition inweight percent comprising the following elemental ranges at leastpartially based on the ranges disclosed in Table 2 and Table 3:

-   -   Fe: BAL    -   B: 0-4 (or about 0 to about 4), C: 0-0.25 (or about 0 to about        0.25), and Si: 0-15 (or about 0 to about 15), where B+C+Si is        4-15 (or about 4 to about 15)    -   Mn: 0-25 (or about 0 to about 25), Mo: 0-29 (or about 0 to about        29), Nb: 0-2 (or about 0 to about 2), Ta: 0-4 (or about 0 to        about 4), Ti: 0-4 (or about 0 to about 4), V: 0-10 (or about 0        to about 10), W: 0-6 (or about 0 to about 6), Zr: 0-10 (about 0        to about 10), where (Mo+Mn+Nb+Ta+Ti+V+W+Zr) is 5-38 (or about 5        to about 38) 0 Cr (or about 0 Cr)

Generally, embodiments of an alloy can be designed using any of thelarge elements as long as the other elemental ratios are controlledproperly. The following atomic sizes, in picometers, were used for thelarge elements, large atoms defined as atoms which are larger than ironatoms: Mn: 161, Mo: 190, Nb, 198, Ta: 200, Ti: 176, V: 171, W: 193, Zr:206. Fe has an atomic size of 156 pm. A large atom can be an atom thatis larger than Fe. These large atoms can be advantageous as they canincrease the viscosity of an alloy in liquid form and thus slow down thecrystallization rate of the alloy. As the crystallization ratedecreases, the probability of forming an amorphous, nanocrystalline, orfine-grained structure can increase.

In some embodiments, the coating can be amorphous. In some embodiments,the coating can be nanocrystalline, as defined by having a grain size of100 nm or less. In some embodiments, the coating can be nanocrystalline,as defined by having a grain size of 50 nm or less. In some embodiments,the coating can be nanocrystalline, as defined by having a grain size of20 nm or less.

In some embodiments, the alloy can be described by a composition inweight percent comprising the following elemental ranges at leastpartially based on a range composed form the alloys selected formanufacture into experimental ingots:

-   -   Fe: BAL, C: 0-0.25 (or about 0 to about 0.25), Mn: 5-19 (or        about 5 to about 19), Mo: 7-23 (or about 7 to about 23), Ni: 0-4        (or about 0 to about 4), Si: 5-10 (or about 5 to about 10)

In some embodiments, the alloy can be described by the specificcompositions, which have been produced and experimentally demonstratedamorphous formation potential, in weight percent, comprising thefollowing elements.

-   -   1. Fe: BAL, Mn: 5 (or about 5), Mo: 23 (or about 23), Si: 10 (or        about 10)    -   2. Fe: BAL, Mn: 5 (or about 5), Mo: 19 (or about 19), Si: 10 (or        about 10)    -   3. Fe: BAL, Mn: 5 (or about 5), Mo: 11 (or about 11), Si: 10 (or        about 10)    -   4. Fe: BAL, Mn: 5 (or about 5), Mo: 13 (or about 13), Si: 10 (or        about 10)    -   5. Fe: BAL, Mn: 5 (or about 5), Mo: 7 (or about 7), Si: 10 (or        about 10)    -   6. Fe: BAL, Al: 2 (or about 2), Mn: 5 (or about 5), Mo: 5 (or        about 5), Si: 13 (or about 13)    -   7. Fe: BAL, Al: 2 (or about 2), Mn: 5 (or about 5), Mo: 7 (or        about 7), Si: 15 (or about 15)    -   8. Fe: BAL, C: 0.25 (or about 0.25), Mn: 19 (or about 19), Mo: 7        (or about 7), Si: (5 or about 5)    -   9. Fe: BAL, C: 0.25 (or about 0.25), Mn: 5 (or about 5), Mo: 7        (or about 7), Ni: (4 or about 4), Si: 5 (or about 5)    -   10. Fe: BAL, Mn: 19 (or about 19), Mo: 7 (or about 7), Si: 7 (or        about 7)    -   11. Fe: BAL, Mn: 19 (or about 19), Mo: 7 (or about 7), Ni: 2 (or        about 2), Si: 5 (or about 5)    -   12. Fe: BAL, Mn: 19 (or about 19), Mo: 15 (or about 15), Si: 6        (or about 6)    -   13. Fe: BAL, Mn: 19 (or about 19), Mo: 7 (or about 7), Ni: 2 (or        about 2), Si: 5 (or about 5)

In some embodiments, aluminum can be further added to the above alloyranges and chemistries to improve coating adhesion in the range of up to5 (or about 5) wt. %. Some exemplary examples of aluminum additions,based upon the #4 and #5 base chemistries, are:

-   -   14. Fe: BAL, Mn: 5 (or about 5), Mo: 13 (or about 13), Si: 10        (or about 10), Al: 2 (or about 2)    -   15. Fe: BAL, Mn: 5 (or about 5), Mo: 7 (or about 7), Si: 10 (or        about 10), Al: 2 (or about 2)

In some embodiments, the alloy may contain boron, such as between 0-4wt. % (including 1, 2, and 3 wt. %) as indicated above. In someembodiments, the alloy may not contain any boron. In some embodiments,boron may act as an impurity and does not exceed 1 wt. %.

The Fe content identified in the composition above may be the balance ofthe composition as indicated above, or alternatively, the balance of thecomposition may comprise Fe and other elements. In some embodiments, thebalance may consist essentially of Fe and may include incidentalimpurities. In some embodiments, the above alloys may not contain anychromium. In some embodiments, chromium may act as an impurity and doesnot exceed 1 wt. %.

Thermodynamic and Kinetic Criteria

In some embodiments, the alloy can be described by thermodynamic andkinetic criteria. In some embodiments, the thermodynamic criteria canrelate to the stability of the liquid phase, e.g., the meltingtemperature of the alloy. The melting temperature can be calculated viathermodynamic models and is defined as the highest temperature at whichliquid is less than 100% of the mole fraction in the material. Thekinetic criterion can be related to the viscosity of the liquid and theconcentration in atom percent of large atoms. Large atoms are defined asatoms which are larger than iron atoms. Either or both criteria can beused to predict the tendency towards amorphous formation in thermalspray materials. In some embodiments, the alloys can have amicrostructure of ferritic iron. In some embodiments, a primarily singlephase fine-grained structure of either martensite, ferrite, or austenitecan be formed. In some embodiments, <5% (or <about 5%) borides andcarbides are formed. In some embodiments, <1% (or <about 1%) borides andcarbides are formed. In some embodiments, <0.1% (or <about 0.1%) boridesand carbides are formed. In some embodiments, no borides or carbides areformed.

In some embodiments, the melting temperature can be below 1500 K (orbelow about 1500K). In some embodiments, the melting temperature can bebelow 1450K (or below about 1450K). In some embodiments, the meltingtemperature can be below 1400K (or below about 1400K). In general,amorphous formation is encouraged with lower melting temperaturesbecause, typically, as grain size decreases, hardness increases (knownas the Hall-Petch relationship). Amorphous alloys effectively have zerograin size, and thus can be the hardest form of the alloy. As amorphousformation potential increases, the alloy, even if it doesn't alwaysbecome amorphous in every process, will tend towards a smaller grainsize. Thus, amorphous forming alloys of the disclosure, even if theyform fine-grained or nanocrystalline structures and not actually anamorphous structure, will tend to be harder. For example, in someembodiments, while there is the potential for an amorphous structure,the alloy may end up being crystalline, specifically nanocrystalline,upon application, such as through thermal spray, while still achievingthe high hardness levels disclosed herein.

In some embodiments, the large atom atomic fraction can be above 5 atom% (or above about 5 atom %). In some embodiments, the large atom atomicfraction can be above 7.5 atom % (or above about 7.5 atom %). In someembodiments, the large atom atomic fraction can be above 10 atom % (orabove about 10 atom %). In some embodiments, the higher large atomatomic fraction can encourage amorphous formation and increase amorphousformation potential.

Table 2 lists the alloy compositions, all Fe-based, in weight percentwhich can meet the thermodynamic criteria detailed in this disclosure.In some embodiments, the Fe-based alloys can have a composition that ispredominantly iron, e.g., at least 50 wt. % iron.

Combining the alloys in Table 2 and Table 3 yields 1,141 compositionswhich meet the criteria. These alloys were compiled throughcomputational searching tools which evaluated 16,362 alloys according tothe disclosed criteria. Thus, the alloys disclosed cover only 6.9% ofthe total explored space explicitly investigated to design an alloy withthe disclosed performance parameters.

TABLE 2 List of alloy compositions with thermodynamic and kineticparameters which meet disclosed criteria. Large atom % is the total atom% of elements larger than iron and melt T is the melting temperature ofthe alloy. Large Melt No B Mn Mo Nb Si Ta Ti V W Zr Atom % T M1 0 0 10 110 0 0 0 0 0 6.1% 1500 M2 0 0 15 1 9 0 0 0 0 0 9.1% 1500 M3 0 0 15 1 100 0 0 0 0 9.0% 1500 M4 0 0 20 0 7 0 0 0 0 0 11.8% 1500 M5 0 0 20 0 8 0 00 0 0 11.7% 1500 M6 0 0 20 0 9 0 0 0 0 0 11.6% 1450 M7 0 0 20 0 10 0 0 00 0 11.5% 1450 M8 0 0 20 1 7 0 0 0 0 0 12.5% 1500 M9 0 0 20 1 8 0 0 0 00 12.3% 1500 M10 0 0 20 1 9 0 0 0 0 0 12.2% 1500 M11 0 0 20 1 10 0 0 0 00 12.1% 1500 M12 0 1 10 0 10 0 0 0 0 0 6.5% 1500 M13 0 1 10 1 10 0 0 0 00 7.1% 1500 M14 0 1 15 1 8 0 0 0 0 0 10.2% 1500 M15 0 1 15 1 9 0 0 0 0 010.1% 1500 M16 0 1 15 1 10 0 0 0 0 0 10.0% 1450 M17 0 1 20 0 7 0 0 0 0 012.8% 1500 M18 0 1 20 0 8 0 0 0 0 0 12.7% 1500 M19 0 1 20 0 9 0 0 0 0 012.6% 1450 M20 0 1 20 0 10 0 0 0 0 0 12.5% 1450 M21 0 1 20 1 7 0 0 0 0 013.5% 1500 M22 0 1 20 1 8 0 0 0 0 0 13.4% 1450 M23 0 1 20 1 9 0 0 0 0 013.2% 1500 M24 0 1 20 1 10 0 0 0 0 0 13.1% 1500 M25 0 2 10 0 10 0 0 0 00 7.4% 1500 M26 0 2 10 1 9 0 0 0 0 0 8.1% 1500 M27 0 2 10 1 10 0 0 0 0 08.0% 1500 M28 0 2 15 1 8 0 0 0 0 0 11.2% 1500 M29 0 2 15 1 9 0 0 0 0 011.1% 1500 M30 0 2 15 1 10 0 0 0 0 0 11.0% 1450 M31 0 2 20 0 7 0 0 0 0 013.9% 1500 M32 0 2 20 0 8 0 0 0 0 0 13.7% 1450 M33 0 2 20 0 9 0 0 0 0 013.6% 1450 M34 0 2 20 0 10 0 0 0 0 0 13.5% 1400 M35 0 2 20 1 6 0 0 0 0 014.7% 1500 M36 0 2 20 1 7 0 0 0 0 0 14.5% 1500 M37 0 2 20 1 8 0 0 0 0 014.4% 1450 M38 0 2 20 1 9 0 0 0 0 0 14.2% 1500 M39 0 2 20 1 10 0 0 0 0 014.1% 1500 M40 0 3 10 0 9 0 0 0 0 0 8.5% 1500 M41 0 3 10 0 10 0 0 0 0 08.4% 1500 M42 0 3 10 1 9 0 0 0 0 0 9.1% 1500 M43 0 3 10 1 10 0 0 0 0 09.0% 1500 M44 0 3 15 1 7 0 0 0 0 0 12.3% 1500 M45 0 3 15 1 8 0 0 0 0 012.2% 1500 M46 0 3 15 1 9 0 0 0 0 0 12.1% 1450 M47 0 3 15 1 10 0 0 0 0 012.0% 1500 M48 0 3 20 0 6 0 0 0 0 0 15.0% 1500 M49 0 3 20 0 8 0 0 0 0 014.7% 1450 M50 0 3 20 1 6 0 0 0 0 0 15.7% 1500 M51 0 3 20 1 8 0 0 0 0 015.4% 1450 M52 0 3 20 1 10 0 0 0 0 0 15.1% 1500 M53 0 4 5 1 10 0 0 0 0 07.1% 1500 M54 0 4 10 0 9 0 0 0 0 0 9.4% 1500 M55 0 4 10 0 10 0 0 0 0 09.3% 1500 M56 0 4 10 1 8 0 0 0 0 0 10.1% 1500 M57 0 4 10 1 9 0 0 0 0 010.0% 1500 M58 0 4 10 1 10 0 0 0 0 0 10.0% 1500 M59 0 4 15 1 7 0 0 0 0 013.4% 1500 M60 0 4 15 1 8 0 0 0 0 0 13.2% 1500 M61 0 4 15 1 9 0 0 0 0 013.1% 1450 M62 0 4 15 1 10 0 0 0 0 0 13.0% 1500 M63 0 4 15 2 6 0 0 0 0 014.1% 1500 M64 0 4 20 0 6 0 0 0 0 0 16.1% 1500 M65 0 4 20 0 7 0 0 0 0 015.9% 1450 M66 0 4 20 0 8 0 0 0 0 0 15.8% 1450 M67 0 4 20 0 9 0 0 0 0 015.6% 1400 M68 0 4 20 0 10 0 0 0 0 0 15.5% 1400 M69 0 4 20 1 5 0 0 0 0 016.9% 1500 M70 0 4 20 1 6 0 0 0 0 0 16.8% 1500 M71 0 4 20 1 7 0 0 0 0 016.6% 1450 M72 0 4 20 1 8 0 0 0 0 0 16.4% 1450 M73 0 4 20 1 9 0 0 0 0 016.3% 1500 M74 0 4 20 1 10 0 0 0 0 0 16.1% 1500 M75 0 4 20 2 5 0 0 0 0 017.6% 1500 M76 0 5 5 1 10 0 0 0 0 0 8.0% 1500 M77 0 5 10 0 8 0 0 0 0 010.5% 1500 M78 0 5 10 0 9 0 0 0 0 0 10.4% 1500 M79 0 5 10 0 10 0 0 0 0 010.3% 1500 M80 0 5 10 1 8 0 0 0 0 0 11.1% 1500 M81 0 5 10 1 9 0 0 0 0 011.0% 1500 M82 0 5 10 1 10 0 0 0 0 0 10.9% 1450 M83 0 5 15 1 6 0 0 0 0 014.5% 1500 M84 0 5 15 1 7 0 0 0 0 0 14.4% 1500 M85 0 5 15 1 8 0 0 0 0 014.2% 1450 M86 0 5 15 1 9 0 0 0 0 0 14.1% 1450 M87 0 5 15 1 10 0 0 0 0 014.0% 1500 M88 0 5 15 2 6 0 0 0 0 0 15.2% 1500 M89 0 5 20 0 5 0 0 0 0 017.3% 1500 M90 0 5 20 0 6 0 0 0 0 0 17.1% 1500 M91 0 5 20 0 7 0 0 0 0 017.0% 1450 M92 0 5 20 0 8 0 0 0 0 0 16.8% 1450 M93 0 5 20 0 9 0 0 0 0 016.6% 1400 M94 0 5 20 0 10 0 0 0 0 0 16.5% 1400 M95 0 5 20 1 5 0 0 0 0 018.0% 1500 M96 0 5 20 1 6 0 0 0 0 0 17.8% 1500 M97 0 5 20 1 7 0 0 0 0 017.6% 1450 M98 0 5 20 1 8 0 0 0 0 0 17.5% 1500 M99 0 5 20 1 9 0 0 0 0 017.3% 1500 M100 0 5 20 1 10 0 0 0 0 0 17.1% 1500 M101 0 5 20 2 5 0 0 0 00 18.7% 1500 M102 4 0 0 0 0 0 0 2 0 6 5.1% 1350 M103 4 0 0 0 0 0 0 2 2 65.7% 1400 M104 4 0 0 0 0 0 0 2 4 4 5.2% 1500 M105 4 0 0 0 0 0 0 2 4 66.3% 1450 M106 4 0 0 0 0 0 0 4 0 4 5.9% 1350 M107 4 0 0 0 0 0 0 4 0 67.0% 1350 M108 4 0 0 0 0 0 0 4 2 2 5.4% 1400 M109 4 0 0 0 0 0 0 4 2 46.5% 1400 M110 4 0 0 0 0 0 0 4 2 6 7.6% 1350 M111 4 0 0 0 0 0 0 4 4 26.0% 1450 M112 4 0 0 0 0 0 0 4 4 4 7.1% 1450 M113 4 0 0 0 0 0 0 4 4 68.3% 1450 M114 4 0 0 0 0 0 0 6 0 0 5.6% 1350 M115 4 0 0 0 0 0 0 6 0 26.7% 1350 M116 4 0 0 0 0 0 0 6 0 4 7.8% 1350 M117 4 0 0 0 0 0 0 6 0 68.9% 1400 M118 4 0 0 0 0 0 0 6 2 0 6.2% 1400 M119 4 0 0 0 0 0 0 6 2 27.3% 1400 M120 4 0 0 0 0 0 0 6 2 4 8.4% 1350 M121 4 0 0 0 0 0 0 6 2 69.6% 1400 M122 4 0 0 0 0 0 0 6 4 0 6.8% 1450 M123 4 0 0 0 0 0 0 6 4 27.9% 1450 M124 4 0 0 0 0 0 0 6 4 4 9.1% 1450 M125 4 0 0 0 0 0 0 6 4 610.2% 1450 M126 4 0 0 0 0 0 0 6 6 0 7.4% 1500 M127 4 0 0 0 0 0 0 6 6 28.6% 1500 M128 4 0 0 0 0 0 0 6 6 4 9.7% 1500 M129 4 0 0 0 0 0 0 6 6 610.9% 1500 M130 4 0 0 0 0 0 0 6 6 8 12.1% 1500 M131 4 0 0 0 0 0 0 6 6 1013.3% 1500 M132 4 0 0 0 0 0 0 8 6 6 12.9% 1500 M133 4 0 0 0 0 0 0 8 6 814.1% 1500 M134 4 0 0 0 0 0 0 8 6 10 15.3% 1500 M135 4 0 0 0 0 0 0 10 66 14.8% 1500 M136 4 0 0 0 0 0 0 10 6 8 16.0% 1500 M137 4 0 0 0 0 0 0 106 10 17.3% 1500 M138 0 3 20 0 10 0 0 0 0 0 14.5% 1400 M139 0 3 20 0 10 00 0 0 2 15.8% 1350 M140 0 3 20 0 10 0 0 0 0 4 17.1% 1350 M141 0 3 20 010 0 0 0 2 0 15.3% 1400 M142 0 3 20 0 10 0 0 0 2 2 16.6% 1400 M143 0 320 0 10 0 0 0 2 4 18.0% 1400 M144 0 3 20 0 10 0 0 0 4 0 16.1% 1450 M1450 3 20 0 10 0 0 0 4 2 17.5% 1450 M146 0 3 20 0 10 0 0 0 4 4 18.9% 1450M147 0 3 20 0 10 0 0 2 0 0 16.6% 1400 M148 0 3 20 0 10 0 0 2 0 2 17.9%1350 M149 0 3 20 0 10 0 0 2 0 4 19.3% 1350 M150 0 3 20 0 10 0 0 2 2 017.4% 1400 M151 0 3 20 0 10 0 0 2 2 2 18.8% 1400 M152 0 3 20 0 10 0 0 22 4 20.2% 1400 M153 0 3 20 0 10 0 0 2 4 0 18.3% 1450 M154 0 3 20 0 10 00 2 4 2 19.7% 1450 M155 0 3 20 0 10 0 0 2 4 4 21.1% 1450 M156 0 3 20 010 0 0 4 0 0 18.7% 1400 M157 0 3 20 0 10 0 0 4 0 2 20.1% 1350 M158 0 320 0 10 0 0 4 0 4 21.4% 1350 M159 0 3 20 0 10 0 0 4 2 0 19.6% 1400 M1600 3 20 0 10 0 0 4 2 2 20.9% 1400 M161 0 3 20 0 10 0 0 4 2 4 22.4% 1400M162 0 3 20 0 10 0 0 4 4 0 20.5% 1450 M163 0 3 20 0 10 0 0 4 4 2 21.9%1450 M164 0 3 20 0 10 0 0 4 4 4 23.3% 1450 M165 0 3 20 0 10 0 2 0 0 016.7% 1400 M166 0 3 20 0 10 0 2 0 0 2 18.0% 1350 M167 0 3 20 0 10 0 2 00 4 19.4% 1350 M168 0 3 20 0 10 0 2 0 2 0 17.5% 1450 M169 0 3 20 0 10 02 0 2 2 18.9% 1450 M170 0 3 20 0 10 0 2 0 2 4 20.3% 1450 M171 0 3 20 010 0 2 0 4 0 18.4% 1500 M172 0 3 20 0 10 0 2 0 4 2 19.8% 1500 M173 0 320 0 10 0 2 0 4 4 21.2% 1500 M174 0 3 20 0 10 0 2 2 0 0 18.8% 1400 M1750 3 20 0 10 0 2 2 0 2 20.2% 1350 M176 0 3 20 0 10 0 2 2 0 4 21.5% 1350M177 0 3 20 0 10 0 2 2 2 0 19.7% 1450 M178 0 3 20 0 10 0 2 2 2 2 21.1%1450 M179 0 3 20 0 10 0 2 2 2 4 22.5% 1450 M180 0 3 20 0 10 0 2 2 4 020.6% 1500 M181 0 3 20 0 10 0 2 2 4 2 22.0% 1500 M182 0 3 20 0 10 0 2 24 4 23.4% 1500 M183 0 3 20 0 10 0 2 4 0 0 20.9% 1400 M184 0 3 20 0 10 02 4 0 2 22.3% 1350 M185 0 3 20 0 10 0 2 4 0 4 23.7% 1350 M186 0 3 20 010 0 2 4 2 0 21.8% 1450 M187 0 3 20 0 10 0 2 4 2 2 23.2% 1450 M188 0 320 0 10 0 2 4 2 4 24.6% 1400 M189 0 3 20 0 10 0 2 4 4 0 22.7% 1450 M1900 3 20 0 10 0 2 4 4 2 24.2% 1450 M191 0 3 20 0 10 0 2 4 4 4 25.6% 1450M192 0 3 20 0 10 0 4 0 0 0 18.9% 1400 M193 0 3 20 0 10 0 4 0 0 2 20.3%1400 M194 0 3 20 0 10 0 4 0 0 4 21.7% 1400 M195 0 3 20 0 10 0 4 0 2 019.8% 1450 M196 0 3 20 0 10 0 4 0 2 2 21.2% 1450 M197 0 3 20 0 10 0 4 02 4 22.6% 1450 M198 0 3 20 0 10 0 4 0 4 0 20.7% 1500 M199 0 3 20 0 10 04 0 4 2 22.1% 1500 M200 0 3 20 0 10 0 4 0 4 4 23.5% 1500 M201 0 3 20 010 0 4 2 0 0 21.0% 1400 M202 0 3 20 0 10 0 4 2 0 2 22.4% 1400 M203 0 320 0 10 0 4 2 0 4 23.8% 1400 M204 0 3 20 0 10 0 4 2 2 0 21.9% 1450 M2050 3 20 0 10 0 4 2 2 2 23.3% 1450 M206 0 3 20 0 10 0 4 2 2 4 24.7% 1450M207 0 3 20 0 10 0 4 2 4 0 22.8% 1500 M208 0 3 20 0 10 0 4 2 4 2 24.3%1500 M209 0 3 20 0 10 0 4 2 4 4 25.7% 1500 M210 0 3 20 0 10 0 4 4 0 023.1% 1400 M211 0 3 20 0 10 0 4 4 0 2 24.5% 1400 M212 0 3 20 0 10 0 4 40 4 25.9% 1400 M213 0 3 20 0 10 0 4 4 2 0 24.1% 1450 M214 0 3 20 0 10 04 4 2 2 25.5% 1450 M215 0 3 20 0 10 0 4 4 2 4 26.9% 1450 M216 0 3 20 010 0 4 4 4 0 25.0% 1500 M217 0 3 20 0 10 0 4 4 4 2 26.4% 1500 M218 0 320 0 10 0 4 4 4 4 27.9% 1500 M219 0 3 20 0 10 2 0 0 0 0 15.3% 1400 M2200 3 20 0 10 2 0 0 0 2 16.6% 1350 M221 0 3 20 0 10 2 0 0 0 4 18.0% 1350M222 0 3 20 0 10 2 0 0 2 0 16.1% 1400 M223 0 3 20 0 10 2 0 0 2 2 17.5%1400 M224 0 3 20 0 10 2 0 0 2 4 18.9% 1400 M225 0 3 20 0 10 2 0 0 4 017.0% 1450 M226 0 3 20 0 10 2 0 0 4 2 18.4% 1500 M227 0 3 20 0 10 2 0 04 4 19.8% 1500 M228 0 3 20 0 10 2 0 2 0 0 17.4% 1400 M229 0 3 20 0 10 20 2 0 2 18.8% 1350 M230 0 3 20 0 10 2 0 2 0 4 20.2% 1350 M231 0 3 20 010 2 0 2 2 0 18.3% 1400 M232 0 3 20 0 10 2 0 2 2 2 19.7% 1400 M233 0 320 0 10 2 0 2 2 4 21.1% 1400 M234 0 3 20 0 10 2 0 2 4 0 19.2% 1450 M2350 3 20 0 10 2 0 2 4 2 20.6% 1450 M236 0 3 20 0 10 2 0 2 4 4 22.0% 1450M237 0 3 20 0 10 2 0 4 0 0 19.6% 1400 M238 0 3 20 0 10 2 0 4 0 2 21.0%1350 M239 0 3 20 0 10 2 0 4 0 4 22.4% 1350 M240 0 3 20 0 10 2 0 4 2 020.5% 1400 M241 0 3 20 0 10 2 0 4 2 2 21.9% 1400 M242 0 3 20 0 10 2 0 42 4 23.3% 1400 M243 0 3 20 0 10 2 0 4 4 0 21.4% 1450 M244 0 3 20 0 10 20 4 4 2 22.8% 1450 M245 0 3 20 0 10 2 0 4 4 4 24.3% 1450 M246 0 3 20 010 2 2 0 0 0 17.5% 1350 M247 0 3 20 0 10 2 2 0 0 2 18.9% 1350 M248 0 320 0 10 2 2 0 0 4 20.3% 1350 M249 0 3 20 0 10 2 2 0 2 0 18.4% 1450 M2500 3 20 0 10 2 2 0 2 2 19.8% 1450 M251 0 3 20 0 10 2 2 0 2 4 21.2% 1450M252 0 3 20 0 10 2 2 0 4 0 19.3% 1500 M253 0 3 20 0 10 2 2 0 4 2 20.7%1500 M254 0 3 20 0 10 2 2 0 4 4 22.1% 1500 M255 0 3 20 0 10 2 2 2 0 019.7% 1350 M256 0 3 20 0 10 2 2 2 0 2 21.1% 1350 M257 0 3 20 0 10 2 2 20 4 22.5% 1350 M258 0 3 20 0 10 2 2 2 2 0 20.6% 1450 M259 0 3 20 0 10 22 2 2 2 22.0% 1450 M260 0 3 20 0 10 2 2 2 2 4 23.4% 1450 M261 0 3 20 010 2 2 2 4 0 21.5% 1500 M262 0 3 20 0 10 2 2 2 4 2 22.9% 1500 M263 0 320 0 10 2 2 2 4 4 24.4% 1500 M264 0 3 20 0 10 2 2 4 0 0 21.8% 1350 M2650 3 20 0 10 2 2 4 0 2 23.2% 1350 M266 0 3 20 0 10 2 2 4 0 4 24.6% 1350M267 0 3 20 0 10 2 2 4 2 0 22.7% 1450 M268 0 3 20 0 10 2 2 4 2 2 24.2%1450 M269 0 3 20 0 10 2 2 4 2 4 25.6% 1450 M270 0 3 20 0 10 2 2 4 4 023.7% 1500 M271 0 3 20 0 10 2 2 4 4 2 25.1% 1500 M272 0 3 20 0 10 2 2 44 4 26.6% 1450 M273 0 3 20 0 10 2 4 0 0 0 19.8% 1400 M274 0 3 20 0 10 24 0 0 2 21.2% 1400 M275 0 3 20 0 10 2 4 0 0 4 22.6% 1400 M276 0 3 20 010 2 4 0 2 0 20.7% 1450 M277 0 3 20 0 10 2 4 0 2 2 22.1% 1450 M278 0 320 0 10 2 4 0 2 4 23.5% 1450 M279 0 3 20 0 10 2 4 0 4 0 21.6% 1500 M2800 3 20 0 10 2 4 0 4 2 23.0% 1500 M281 0 3 20 0 10 2 4 0 4 4 24.5% 1500M282 0 3 20 0 10 2 4 2 0 0 21.9% 1400 M283 0 3 20 0 10 2 4 2 0 2 23.3%1400 M284 0 3 20 0 10 2 4 2 0 4 24.7% 1400 M285 0 3 20 0 10 2 4 2 2 022.9% 1450 M286 0 3 20 0 10 2 4 2 2 2 24.3% 1450 M287 0 3 20 0 10 2 4 22 4 25.7% 1450 M288 0 3 20 0 10 2 4 2 4 0 23.8% 1500 M289 0 3 20 0 10 24 2 4 2 25.2% 1500 M290 0 3 20 0 10 2 4 2 4 4 26.7% 1500 M291 0 3 20 010 2 4 4 0 0 24.1% 1400 M292 0 3 20 0 10 2 4 4 0 2 25.5% 1400 M293 0 320 0 10 2 4 4 0 4 26.9% 1400 M294 0 3 20 0 10 2 4 4 2 0 25.0% 1450 M2950 3 20 0 10 2 4 4 2 2 26.4% 1450 M296 0 3 20 0 10 2 4 4 2 4 27.9% 1450M297 0 3 20 0 10 2 4 4 4 0 26.0% 1500 M298 0 3 20 0 10 2 4 4 4 2 27.4%1500 M299 0 3 20 0 10 2 4 4 4 4 28.9% 1500 M300 0 3 20 0 10 4 0 0 0 016.1% 1350 M301 0 3 20 0 10 4 0 0 0 2 17.5% 1350 M302 0 3 20 0 10 4 0 00 4 18.9% 1350 M303 0 3 20 0 10 4 0 0 2 0 17.0% 1400 M304 0 3 20 0 10 40 0 2 2 18.4% 1400 M305 0 3 20 0 10 4 0 0 2 4 19.8% 1450 M306 0 3 20 010 4 0 0 4 0 17.8% 1500 M307 0 3 20 0 10 4 0 0 4 2 19.3% 1500 M308 0 320 0 10 4 0 0 4 4 20.7% 1500 M309 0 3 20 0 10 4 0 2 0 0 18.3% 1350 M3100 3 20 0 10 4 0 2 0 2 19.7% 1350 M311 0 3 20 0 10 4 0 2 0 4 21.1% 1350M312 0 3 20 0 10 4 0 2 2 0 19.2% 1400 M313 0 3 20 0 10 4 0 2 2 2 20.6%1400 M314 0 3 20 0 10 4 0 2 2 4 22.0% 1400 M315 0 3 20 0 10 4 0 2 4 020.1% 1450 M316 0 3 20 0 10 4 0 2 4 2 21.5% 1450 M317 0 3 20 0 10 4 0 24 4 23.0% 1450 M318 0 3 20 0 10 4 0 4 0 0 20.5% 1350 M319 0 3 20 0 10 40 4 0 2 21.9% 1350 M320 0 3 20 0 10 4 0 4 0 4 23.3% 1350 M321 0 3 20 010 4 0 4 2 0 21.4% 1400 M322 0 3 20 0 10 4 0 4 2 2 22.8% 1400 M323 0 320 0 10 4 0 4 2 4 24.3% 1400 M324 0 3 20 0 10 4 0 4 4 0 22.3% 1450 M3250 3 20 0 10 4 0 4 4 2 23.8% 1450 M326 0 3 20 0 10 4 0 4 4 4 25.3% 1450M327 0 3 20 0 10 4 2 0 0 0 18.4% 1350 M328 0 3 20 0 10 4 2 0 0 2 19.8%1400 M329 0 3 20 0 10 4 2 0 0 4 21.2% 1400 M330 0 3 20 0 10 4 2 0 2 019.3% 1450 M331 0 3 20 0 10 4 2 0 2 2 20.7% 1450 M332 0 3 20 0 10 4 2 02 4 22.2% 1450 M333 0 3 20 0 10 4 2 0 4 0 20.2% 1500 M334 0 3 20 0 10 42 0 4 2 21.7% 1500 M335 0 3 20 0 10 4 2 0 4 4 23.1% 1500 M336 0 3 20 010 4 2 2 0 0 20.6% 1350 M337 0 3 20 0 10 4 2 2 0 2 22.0% 1350 M338 0 320 0 10 4 2 2 0 4 23.4% 1350 M339 0 3 20 0 10 4 2 2 2 0 21.5% 1450 M3400 3 20 0 10 4 2 2 2 2 22.9% 1450 M341 0 3 20 0 10 4 2 2 2 4 24.4% 1450M342 0 3 20 0 10 4 2 2 4 0 22.4% 1500 M343 0 3 20 0 10 4 2 2 4 2 23.9%1500 M344 0 3 20 0 10 4 2 2 4 4 25.4% 1500 M345 0 3 20 0 10 4 2 4 0 022.7% 1350 M346 0 3 20 0 10 4 2 4 0 2 24.2% 1350 M347 0 3 20 0 10 4 2 40 4 25.6% 1350 M348 0 3 20 0 10 4 2 4 2 0 23.7% 1450 M349 0 3 20 0 10 42 4 2 2 25.1% 1450 M350 0 3 20 0 10 4 2 4 2 4 26.6% 1450 M351 0 3 20 010 4 2 4 4 0 24.7% 1500 M352 0 3 20 0 10 4 2 4 4 2 26.1% 1500 M353 0 320 0 10 4 2 4 4 4 27.6% 1450 M354 0 3 20 0 10 4 4 0 0 0 20.7% 1400 M3550 3 20 0 10 4 4 0 0 2 22.1% 1400 M356 0 3 20 0 10 4 4 0 0 4 23.5% 1400M357 0 3 20 0 10 4 4 0 2 0 21.6% 1500 M358 0 3 20 0 10 4 4 0 2 2 23.0%1500 M359 0 3 20 0 10 4 4 0 2 4 24.5% 1450 M360 0 3 20 0 10 4 4 0 4 224.0% 1500 M361 0 3 20 0 10 4 4 0 4 4 25.5% 1500 M362 0 3 20 0 10 4 4 20 0 22.9% 1400 M363 0 3 20 0 10 4 4 2 0 2 24.3% 1400 M364 0 3 20 0 10 44 2 0 4 25.7% 1400 M365 0 3 20 0 10 4 4 2 2 0 23.8% 1450 M366 0 3 20 010 4 4 2 2 2 25.2% 1450 M367 0 3 20 0 10 4 4 2 2 4 26.7% 1450 M368 0 320 0 10 4 4 2 4 0 24.8% 1500 M369 0 3 20 0 10 4 4 2 4 2 26.2% 1500 M3700 3 20 0 10 4 4 2 4 4 27.7% 1500 M371 0 3 20 0 10 4 4 4 0 0 25.0% 1400M372 0 3 20 0 10 4 4 4 0 2 26.4% 1400 M373 0 3 20 0 10 4 4 4 0 4 27.9%1400 M374 0 3 20 0 10 4 4 4 2 0 26.0% 1450 M375 0 3 20 0 10 4 4 4 2 227.4% 1450 M376 0 3 20 0 10 4 4 4 2 4 28.9% 1450 M377 0 3 20 0 10 4 4 44 0 27.0% 1500 M378 0 3 20 0 10 4 4 4 4 2 28.5% 1500 M379 0 3 20 0 7 0 00 0 0 14.9% 1500 M380 0 3 20 0 9 0 0 0 0 0 14.6% 1450 M381 0 3 20 0 11 00 0 0 0 14.3% 1400 M382 0 3 20 0 13 0 0 0 0 0 14.1% 1400 M383 0 3 20 015 0 0 0 0 0 13.8% 1450 M384 0 3 20 1 7 0 0 0 0 0 15.6% 1450 M385 0 3 201 9 0 0 0 0 0 15.3% 1500 M386 0 3 20 1 11 0 0 0 0 0 15.0% 1500 M387 0 320 2 5 0 0 0 0 0 16.6% 1500 M388 0 0 11 0 10 0 0 0 0 0 6.1% 1500 M389 00 13 0 10 0 0 0 0 0 7.2% 1500 M390 0 0 15 0 9 0 0 0 0 0 8.5% 1500 M391 00 15 0 10 0 0 0 0 0 8.4% 1500 M392 0 0 17 0 8 0 0 0 0 0 9.8% 1500 M393 00 17 0 9 0 0 0 0 0 9.7% 1500 M394 0 0 17 0 10 0 0 0 0 0 9.6% 1450 M395 00 19 0 8 0 0 0 0 0 11.1% 1500 M396 0 0 19 0 9 0 0 0 0 0 11.0% 1500 M3970 0 19 0 10 0 0 0 0 0 10.8% 1450 M398 0 0 21 0 7 0 0 0 0 0 12.5% 1500M399 0 0 21 0 8 0 0 0 0 0 12.3% 1500 M400 0 0 21 0 9 0 0 0 0 0 12.2%1450 M401 0 0 21 0 10 0 0 0 0 0 12.1% 1450 M402 0 0 23 0 7 0 0 0 0 013.8% 1500 M403 0 0 23 0 8 0 0 0 0 0 13.6% 1450 M404 0 0 23 0 9 0 0 0 00 13.5% 1450 M405 0 0 23 0 10 0 0 0 0 0 13.3% 1400 M406 0 0 25 0 6 0 0 00 0 15.2% 1500 M407 0 0 25 0 7 0 0 0 0 0 15.1% 1500 M408 0 0 25 0 8 0 00 0 0 14.9% 1450 M409 0 0 25 0 9 0 0 0 0 0 14.8% 1400 M410 0 0 25 0 10 00 0 0 0 14.6% 1400 M411 0 0 27 0 6 0 0 0 0 0 16.6% 1500 M412 0 0 27 0 70 0 0 0 0 16.4% 1450 M413 0 0 27 0 8 0 0 0 0 0 16.3% 1450 M414 0 0 27 09 0 0 0 0 0 16.1% 1400 M415 0 0 27 0 10 0 0 0 0 0 15.9% 1400 M416 0 0 290 5 0 0 0 0 0 18.2% 1500 M417 0 0 29 0 6 0 0 0 0 0 18.0% 1500 M418 0 029 0 7 0 0 0 0 0 17.8% 1450 M419 0 0 29 0 8 0 0 0 0 0 17.6% 1400 M420 00 29 0 9 0 0 0 0 0 17.4% 1400 M421 0 0 29 0 10 0 0 0 0 0 17.3% 1400 M4220 1 11 0 10 0 0 0 0 0 7.0% 1500 M423 0 1 13 0 9 0 0 0 0 0 8.3% 1500 M4240 1 13 0 10 0 0 0 0 0 8.2% 1500 M425 0 1 15 0 9 0 0 0 0 0 9.5% 1500 M4260 1 15 0 10 0 0 0 0 0 9.4% 1500 M427 0 1 17 0 8 0 0 0 0 0 10.8% 1500M428 0 1 17 0 9 0 0 0 0 0 10.7% 1500 M429 0 1 17 0 10 0 0 0 0 0 10.6%1450 M430 0 1 19 0 7 0 0 0 0 0 12.2% 1500 M431 0 1 19 0 8 0 0 0 0 012.1% 1500 M432 0 1 19 0 9 0 0 0 0 0 12.0% 1450 M433 0 1 19 0 10 0 0 0 00 11.8% 1450 M434 0 1 21 0 7 0 0 0 0 0 13.5% 1500 M435 0 1 21 0 8 0 0 00 0 13.4% 1450 M436 0 1 21 0 9 0 0 0 0 0 13.2% 1450 M437 0 1 21 0 10 0 00 0 0 13.1% 1400 M438 0 1 23 0 6 0 0 0 0 0 14.9% 1500 M439 0 1 23 0 7 00 0 0 0 14.8% 1500 M440 0 1 23 0 8 0 0 0 0 0 14.6% 1450 M441 0 1 23 0 90 0 0 0 0 14.5% 1450 M442 0 1 23 0 10 0 0 0 0 0 14.4% 1400 M443 0 1 25 06 0 0 0 0 0 16.3% 1500 M444 0 1 25 0 7 0 0 0 0 0 16.1% 1450 M445 0 1 250 8 0 0 0 0 0 16.0% 1450 M446 0 1 25 0 9 0 0 0 0 0 15.8% 1400 M447 0 125 0 10 0 0 0 0 0 15.7% 1400 M448 0 1 27 0 5 0 0 0 0 0 17.9% 1500 M449 01 27 0 6 0 0 0 0 0 17.7% 1500 M450 0 1 27 0 7 0 0 0 0 0 17.5% 1450 M4510 1 27 0 8 0 0 0 0 0 17.3% 1400 M452 0 1 27 0 9 0 0 0 0 0 17.1% 1400M453 0 1 27 0 10 0 0 0 0 0 17.0% 1400 M454 0 1 29 0 5 0 0 0 0 0 19.3%1500 M455 0 1 29 0 6 0 0 0 0 0 19.1% 1450 M456 0 1 29 0 7 0 0 0 0 018.9% 1450 M457 0 1 29 0 8 0 0 0 0 0 18.7% 1400 M458 0 1 29 0 9 0 0 0 00 18.5% 1400 M459 0 1 29 0 10 0 0 0 0 0 18.3% 1400 M460 0 2 9 0 10 0 0 00 0 6.8% 1500 M461 0 2 11 0 9 0 0 0 0 0 8.1% 1500 M462 0 2 11 0 10 0 0 00 0 8.0% 1500 M463 0 2 13 0 9 0 0 0 0 0 9.3% 1500 M464 0 2 13 0 10 0 0 00 0 9.2% 1500 M465 0 2 15 0 8 0 0 0 0 0 10.6% 1500 M466 0 2 15 0 9 0 0 00 0 10.5% 1500 M467 0 2 15 0 10 0 0 0 0 0 10.4% 1450 M468 0 2 17 0 7 0 00 0 0 11.9% 1500 M469 0 2 17 0 8 0 0 0 0 0 11.8% 1500 M470 0 2 17 0 9 00 0 0 0 11.7% 1450 M471 0 2 17 0 10 0 0 0 0 0 11.6% 1450 M472 0 2 19 0 70 0 0 0 0 13.2% 1500 M473 0 2 19 0 8 0 0 0 0 0 13.1% 1500 M474 0 2 19 09 0 0 0 0 0 13.0% 1450 M475 0 2 19 0 10 0 0 0 0 0 12.8% 1450 M476 0 2 210 6 0 0 0 0 0 14.7% 1500 M477 0 2 21 0 7 0 0 0 0 0 14.5% 1500 M478 0 221 0 8 0 0 0 0 0 14.4% 1450 M479 0 2 21 0 9 0 0 0 0 0 14.2% 1450 M480 02 21 0 10 0 0 0 0 0 14.1% 1400 M481 0 2 23 0 6 0 0 0 0 0 16.0% 1500 M4820 2 23 0 7 0 0 0 0 0 15.8% 1450 M483 0 2 23 0 8 0 0 0 0 0 15.7% 1450M484 0 2 23 0 9 0 0 0 0 0 15.5% 1400 M485 0 2 23 0 10 0 0 0 0 0 15.4%1400 M486 0 2 25 0 5 0 0 0 0 0 17.5% 1500 M487 0 2 25 0 6 0 0 0 0 017.4% 1500 M488 0 2 25 0 7 0 0 0 0 0 17.2% 1450 M489 0 2 25 0 8 0 0 0 00 17.0% 1400 M490 0 2 25 0 9 0 0 0 0 0 16.8% 1400 M491 0 2 25 0 10 0 0 00 0 16.7% 1350 M492 0 2 27 0 5 0 0 0 0 0 18.9% 1500 M493 0 2 27 0 6 0 00 0 0 18.7% 1450 M494 0 2 27 0 7 0 0 0 0 0 18.6% 1450 M495 0 2 27 0 8 00 0 0 0 18.4% 1400 M496 0 2 27 0 9 0 0 0 0 0 18.2% 1400 M497 0 2 27 0 100 0 0 0 0 18.0% 1400 M498 0 2 29 0 5 0 0 0 0 0 20.4% 1500 M499 0 2 29 06 0 0 0 0 0 20.2% 1450 M500 0 2 29 0 7 0 0 0 0 0 19.9% 1400 M501 0 2 290 8 0 0 0 0 0 19.7% 1400 M502 0 2 29 0 9 0 0 0 0 0 19.5% 1400 M503 0 229 0 10 0 0 0 0 0 19.3% 1400 M504 0 3 7 0 10 0 0 0 0 0 6.7% 1500 M505 03 9 0 10 0 0 0 0 0 7.8% 1500 M506 0 3 11 0 9 0 0 0 0 0 9.1% 1500 M507 03 11 0 10 0 0 0 0 0 9.0% 1500 M508 0 3 13 0 8 0 0 0 0 0 10.4% 1500 M5090 3 13 0 9 0 0 0 0 0 10.3% 1500 M510 0 3 13 0 10 0 0 0 0 0 10.2% 1450M511 0 3 15 0 8 0 0 0 0 0 11.6% 1500 M512 0 3 15 0 9 0 0 0 0 0 11.5%1500 M513 0 3 15 0 10 0 0 0 0 0 11.4% 1450 M514 0 3 17 0 7 0 0 0 0 013.0% 1500 M515 0 3 17 0 8 0 0 0 0 0 12.8% 1500 M516 0 3 17 0 9 0 0 0 00 12.7% 1450 M517 0 3 17 0 10 0 0 0 0 0 12.6% 1450 M518 0 3 19 0 6 0 0 00 0 14.4% 1500 M519 0 3 19 0 7 0 0 0 0 0 14.2% 1500 M520 0 3 19 0 8 0 00 0 0 14.1% 1450 M521 0 3 19 0 9 0 0 0 0 0 14.0% 1450 M522 0 3 19 0 10 00 0 0 0 13.8% 1400 M523 0 3 21 0 6 0 0 0 0 0 15.7% 1500 M524 0 3 21 0 70 0 0 0 0 15.6% 1500 M525 0 3 21 0 8 0 0 0 0 0 15.4% 1450 M526 0 3 21 09 0 0 0 0 0 15.2% 1400 M527 0 3 21 0 10 0 0 0 0 0 15.1% 1400 M528 0 3 230 5 0 0 0 0 0 17.2% 1500 M529 0 3 23 0 6 0 0 0 0 0 17.1% 1500 M530 0 323 0 7 0 0 0 0 0 16.9% 1450 M531 0 3 23 0 8 0 0 0 0 0 16.7% 1450 M532 03 23 0 9 0 0 0 0 0 16.5% 1400 M533 0 3 23 0 10 0 0 0 0 0 16.4% 1400 M5340 3 25 0 5 0 0 0 0 0 18.6% 1500 M535 0 3 25 0 6 0 0 0 0 0 18.4% 1450M536 0 3 25 0 7 0 0 0 0 0 18.2% 1450 M537 0 3 25 0 8 0 0 0 0 0 18.0%1400 M538 0 3 25 0 9 0 0 0 0 0 17.9% 1400 M539 0 3 25 0 10 0 0 0 0 017.7% 1350 M540 0 3 27 0 5 0 0 0 0 0 20.0% 1500 M541 0 3 27 0 6 0 0 0 00 19.8% 1450 M542 0 3 27 0 7 0 0 0 0 0 19.6% 1400 M543 0 3 27 0 8 0 0 00 0 19.4% 1400 M544 0 3 27 0 9 0 0 0 0 0 19.2% 1350 M545 0 3 27 0 10 0 00 0 0 19.0% 1400 M546 0 3 29 0 4 0 0 0 0 0 21.7% 1500 M547 0 3 29 0 5 00 0 0 0 21.5% 1500 M548 0 3 29 0 6 0 0 0 0 0 21.2% 1450 M549 0 3 29 0 70 0 0 0 0 21.0% 1400 M550 0 3 29 0 8 0 0 0 0 0 20.8% 1400 M551 0 3 29 09 0 0 0 0 0 20.6% 1400 M552 0 3 29 0 10 0 0 0 0 0 20.4% 1400 M553 0 4 70 10 0 0 0 0 0 7.6% 1500 M554 0 4 9 0 9 0 0 0 0 0 8.8% 1500 M555 0 4 9 010 0 0 0 0 0 8.8% 1500 M556 0 4 11 0 9 0 0 0 0 0 10.0% 1500 M557 0 4 110 10 0 0 0 0 0 9.9% 1500 M558 0 4 13 0 8 0 0 0 0 0 11.3% 1500 M559 0 413 0 9 0 0 0 0 0 11.2% 1500 M560 0 4 13 0 10 0 0 0 0 0 11.1% 1450 M561 04 15 0 7 0 0 0 0 0 12.7% 1500 M562 0 4 15 0 8 0 0 0 0 0 12.6% 1500 M5630 4 15 0 9 0 0 0 0 0 12.5% 1450 M564 0 4 15 0 10 0 0 0 0 0 12.3% 1450M565 0 4 17 0 7 0 0 0 0 0 14.0% 1500 M566 0 4 17 0 8 0 0 0 0 0 13.8%1450 M567 0 4 17 0 9 0 0 0 0 0 13.7% 1450 M568 0 4 17 0 10 0 0 0 0 013.6% 1400 M569 0 4 19 0 6 0 0 0 0 0 15.4% 1500 M570 0 4 19 0 7 0 0 0 00 15.3% 1500 M571 0 4 19 0 8 0 0 0 0 0 15.1% 1450 M572 0 4 19 0 9 0 0 00 0 15.0% 1450 M573 0 4 19 0 10 0 0 0 0 0 14.8% 1400 M574 0 4 21 0 6 0 00 0 0 16.8% 1500 M575 0 4 21 0 7 0 0 0 0 0 16.6% 1450 M576 0 4 21 0 8 00 0 0 0 16.4% 1450 M577 0 4 21 0 9 0 0 0 0 0 16.3% 1400 M578 0 4 21 0 100 0 0 0 0 16.1% 1400 M579 0 4 23 0 5 0 0 0 0 0 18.3% 1500 M580 0 4 23 06 0 0 0 0 0 18.1% 1500 M581 0 4 23 0 7 0 0 0 0 0 17.9% 1450 M582 0 4 230 8 0 0 0 0 0 17.7% 1400 M583 0 4 23 0 9 0 0 0 0 0 17.6% 1400 M584 0 423 0 10 0 0 0 0 0 17.4% 1350 M585 0 4 25 0 5 0 0 0 0 0 19.7% 1500 M586 04 25 0 6 0 0 0 0 0 19.5% 1450 M587 0 4 25 0 7 0 0 0 0 0 19.3% 1450 M5880 4 25 0 8 0 0 0 0 0 19.1% 1400 M589 0 4 25 0 9 0 0 0 0 0 18.9% 1350M590 0 4 25 0 10 0 0 0 0 0 18.7% 1350 M591 0 4 27 0 4 0 0 0 0 0 21.3%1500 M592 0 4 27 0 5 0 0 0 0 0 21.1% 1500 M593 0 4 27 0 6 0 0 0 0 020.9% 1450 M594 0 4 27 0 7 0 0 0 0 0 20.7% 1400 M595 0 4 27 0 8 0 0 0 00 20.5% 1400 M596 0 4 27 0 9 0 0 0 0 0 20.2% 1350 M597 0 4 27 0 10 0 0 00 0 20.0% 1400 M598 0 4 29 0 4 0 0 0 0 0 22.8% 1500 M599 0 4 29 0 5 0 00 0 0 22.5% 1450 M600 0 4 29 0 6 0 0 0 0 0 22.3% 1450 M601 0 4 29 0 7 00 0 0 0 22.1% 1400 M602 0 4 29 0 8 0 0 0 0 0 21.8% 1400 M603 0 4 29 0 90 0 0 0 0 21.6% 1400 M604 0 4 29 0 10 0 0 0 0 0 21.4% 1400 M605 0 5 5 010 0 0 0 0 0 7.4% 1500 M606 0 5 7 0 10 0 0 0 0 0 8.6% 1500 M607 0 5 9 09 0 0 0 0 0 9.8% 1500 M608 0 5 9 0 10 0 0 0 0 0 9.7% 1500 M609 0 5 11 08 0 0 0 0 0 11.1% 1500 M610 0 5 11 0 9 0 0 0 0 0 11.0% 1500 M611 0 5 110 10 0 0 0 0 0 10.9% 1450 M612 0 5 13 0 7 0 0 0 0 0 12.5% 1500 M613 0 513 0 8 0 0 0 0 0 12.3% 1500 M614 0 5 13 0 9 0 0 0 0 0 12.2% 1450 M615 05 13 0 10 0 0 0 0 0 12.1% 1450 M616 0 5 15 0 7 0 0 0 0 0 13.7% 1500 M6170 5 15 0 8 0 0 0 0 0 13.6% 1500 M618 0 5 15 0 9 0 0 0 0 0 13.4% 1450M619 0 5 15 0 10 0 0 0 0 0 13.3% 1450 M620 0 5 17 0 6 0 0 0 0 0 15.1%1500 M621 0 5 17 0 7 0 0 0 0 0 15.0% 1500 M622 0 5 17 0 8 0 0 0 0 014.8% 1450 M623 0 5 17 0 9 0 0 0 0 0 14.7% 1450 M624 0 5 17 0 10 0 0 0 00 14.6% 1400 M625 0 5 19 0 6 0 0 0 0 0 16.5% 1500 M626 0 5 19 0 7 0 0 00 0 16.3% 1450 M627 0 5 19 0 8 0 0 0 0 0 16.1% 1450 M628 0 5 19 0 9 0 00 0 0 16.0% 1400 M629 0 5 19 0 10 0 0 0 0 0 15.8% 1400 M630 0 5 21 0 5 00 0 0 0 18.0% 1500 M631 0 5 21 0 6 0 0 0 0 0 17.8% 1500 M632 0 5 21 0 70 0 0 0 0 17.6% 1450 M633 0 5 21 0 8 0 0 0 0 0 17.4% 1450 M634 0 5 21 09 0 0 0 0 0 17.3% 1400 M635 0 5 21 0 10 0 0 0 0 0 17.1% 1400 M636 0 5 230 5 0 0 0 0 0 19.4% 1500 M637 0 5 23 0 6 0 0 0 0 0 19.2% 1450 M638 0 523 0 7 0 0 0 0 0 19.0% 1450 M639 0 5 23 0 8 0 0 0 0 0 18.8% 1400 M640 05 23 0 9 0 0 0 0 0 18.6% 1400 M641 0 5 23 0 10 0 0 0 0 0 18.4% 1350 M6420 5 25 0 4 0 0 0 0 0 21.0% 1500 M643 0 5 25 0 5 0 0 0 0 0 20.8% 1500M644 0 5 25 0 6 0 0 0 0 0 20.5% 1450 M645 0 5 25 0 7 0 0 0 0 0 20.3%1400 M646 0 5 25 0 8 0 0 0 0 0 20.1% 1400 M647 0 5 25 0 9 0 0 0 0 019.9% 1350 M648 0 5 25 0 10 0 0 0 0 0 19.7% 1350 M649 0 5 27 0 4 0 0 0 00 22.4% 1500 M650 0 5 27 0 5 0 0 0 0 0 22.2% 1450 M651 0 5 27 0 6 0 0 00 0 22.0% 1450 M652 0 5 27 0 7 0 0 0 0 0 21.7% 1400 M653 0 5 27 0 8 0 00 0 0 21.5% 1350 M654 0 5 27 0 9 0 0 0 0 0 21.3% 1350 M655 0 5 27 0 10 00 0 0 0 21.1% 1400 M656 0 5 29 0 4 0 0 0 0 0 23.9% 1500 M657 0 5 29 0 50 0 0 0 0 23.6% 1450 M658 0 5 29 0 6 0 0 0 0 0 23.4% 1400 M659 0 5 29 07 0 0 0 0 0 23.1% 1400 M660 0 5 29 0 8 0 0 0 0 0 22.9% 1400 M661 0 5 290 9 0 0 0 0 0 22.7% 1400 M662 0 5 29 0 10 0 0 0 0 0 22.4% 1400 M663 0 55 0 10 1 1 1 1 1 10.8% 1450 M664 0 5 5 0 10 0 0 0 1 0 7.7% 1500 M665 0 55 0 10 0 0 0 2 0 8.1% 1500 M666 0 5 5 0 10 0 0 0 3 0 8.4% 1500 M667 0 55 0 10 0 0 0 4 0 8.8% 1500 M668 0 5 5 0 10 0 0 1 0 0 8.4% 1500 M669 0 55 0 10 0 0 1 1 0 8.8% 1500 M670 0 5 5 0 10 0 0 1 2 0 9.1% 1500 M671 0 55 0 10 0 0 1 3 0 9.4% 1500 M672 0 5 5 0 10 0 0 1 4 0 9.8% 1500 M673 0 55 0 10 0 0 2 0 0 9.4% 1500 M674 0 5 5 0 10 0 0 2 1 0 9.8% 1500 M675 0 55 0 10 0 0 2 2 0 10.1% 1500 M676 0 5 5 0 10 0 0 2 3 0 10.5% 1500 M677 05 5 0 10 0 0 2 4 0 10.8% 1500 M678 0 5 5 0 10 0 0 3 0 0 10.4% 1500 M6790 5 5 0 10 0 0 3 1 0 10.8% 1500 M680 0 5 5 0 10 0 0 3 2 0 11.1% 1500M681 0 5 5 0 10 0 0 3 3 0 11.5% 1500 M682 0 5 5 0 10 0 0 3 4 0 11.9%1500 M683 0 5 5 0 10 0 0 4 0 0 11.4% 1500 M684 0 5 5 0 10 0 0 4 1 011.8% 1500 M685 0 5 5 0 10 0 0 4 2 0 12.2% 1500 M686 0 5 5 0 10 0 0 4 30 12.5% 1500 M687 0 5 5 0 10 0 0 4 4 0 12.9% 1500 M688 0 5 5 0 10 0 1 00 0 8.5% 1500 M689 0 5 5 0 10 0 1 0 1 0 8.8% 1500 M690 0 5 5 0 10 0 1 02 0 9.2% 1500 M691 0 5 5 0 10 0 1 0 3 0 9.5% 1500 M692 0 5 5 0 10 0 1 04 0 9.9% 1500 M693 0 5 5 0 10 0 1 1 0 0 9.5% 1500 M694 0 5 5 0 10 0 1 11 0 9.8% 1500 M695 0 5 5 0 10 0 1 1 2 0 10.2% 1500 M696 0 5 5 0 10 0 1 13 0 10.5% 1500 M697 0 5 5 0 10 0 1 1 4 0 10.9% 1500 M698 0 5 5 0 10 0 12 0 0 10.5% 1500 M699 0 5 5 0 10 0 1 2 1 0 10.8% 1500 M700 0 5 5 0 10 01 2 2 0 11.2% 1500 M701 0 5 5 0 10 0 1 2 3 0 11.6% 1500 M702 0 5 5 0 100 1 2 4 0 11.9% 1500 M703 0 5 5 0 10 0 1 3 0 0 11.5% 1500 M704 0 5 5 010 0 1 3 1 0 11.8% 1500 M705 0 5 5 0 10 0 1 3 2 0 12.2% 1500 M706 0 5 50 10 0 1 3 3 0 12.6% 1500 M707 0 5 5 0 10 0 1 3 4 0 12.9% 1450 M708 0 55 0 10 0 1 4 0 0 12.5% 1500 M709 0 5 5 0 10 0 1 4 1 0 12.9% 1500 M710 05 5 0 10 0 1 4 2 0 13.2% 1500 M711 0 5 5 0 10 0 1 4 3 0 13.6% 1500 M7120 5 5 0 10 0 1 4 4 0 14.0% 1450 M713 0 5 5 0 10 0 2 0 0 0 9.5% 1500 M7140 5 5 0 10 0 2 0 1 0 9.9% 1500 M715 0 5 5 0 10 0 2 0 2 0 10.2% 1500 M7160 5 5 0 10 0 2 0 3 0 10.6% 1450 M717 0 5 5 0 10 0 2 0 4 0 10.9% 1450M718 0 5 5 0 10 0 2 1 0 0 10.5% 1500 M719 0 5 5 0 10 0 2 1 1 0 10.9%1500 M720 0 5 5 0 10 0 2 1 2 0 11.3% 1500 M721 0 5 5 0 10 0 2 1 3 011.6% 1450 M722 0 5 5 0 10 0 2 1 4 0 12.0% 1450 M723 0 5 5 0 10 0 2 2 00 11.5% 1500 M724 0 5 5 0 10 0 2 2 1 0 11.9% 1500 M725 0 5 5 0 10 0 2 22 0 12.3% 1500 M726 0 5 5 0 10 0 2 2 3 0 12.6% 1450 M727 0 5 5 0 10 0 22 4 0 13.0% 1450 M728 0 5 5 0 10 0 2 3 0 0 12.5% 1500 M729 0 5 5 0 10 02 3 1 0 12.9% 1500 M730 0 5 5 0 10 0 2 3 2 0 13.3% 1450 M731 0 5 5 0 100 2 3 3 0 13.7% 1450 M732 0 5 5 0 10 0 2 3 4 0 14.0% 1450 M733 0 5 5 010 0 2 4 0 0 13.5% 1500 M734 0 5 5 0 10 0 2 4 1 0 13.9% 1500 M735 0 5 50 10 0 2 4 2 0 14.3% 1450 M736 0 5 5 0 10 0 2 4 3 0 14.7% 1450 M737 0 55 0 10 0 2 4 4 0 15.1% 1450 M738 0 5 5 0 10 0 3 0 0 0 10.6% 1500 M739 05 5 0 10 0 3 0 1 0 11.0% 1450 M740 0 5 5 0 10 0 3 0 2 0 11.3% 1450 M7410 5 5 0 10 0 3 0 3 0 11.7% 1450 M742 0 5 5 0 10 0 3 0 4 0 12.0% 1450M743 0 5 5 0 10 0 3 1 0 0 11.6% 1500 M744 0 5 5 0 10 0 3 1 1 0 12.0%1450 M745 0 5 5 0 10 0 3 1 2 0 12.3% 1450 M746 0 5 5 0 10 0 3 1 3 012.7% 1450 M747 0 5 5 0 10 0 3 1 4 0 13.1% 1450 M748 0 5 5 0 10 0 3 2 00 12.6% 1450 M749 0 5 5 0 10 0 3 2 1 0 13.0% 1450 M750 0 5 5 0 10 0 3 22 0 13.3% 1450 M751 0 5 5 0 10 0 3 2 3 0 13.7% 1450 M752 0 5 5 0 10 0 32 4 0 14.1% 1450 M753 0 5 5 0 10 0 3 3 0 0 13.6% 1450 M754 0 5 5 0 10 03 3 1 0 14.0% 1450 M755 0 5 5 0 10 0 3 3 2 0 14.3% 1450 M756 0 5 5 0 100 3 3 3 0 14.7% 1450 M757 0 5 5 0 10 0 3 3 4 0 15.1% 1450 M758 0 5 5 010 0 3 4 0 0 14.6% 1450 M759 0 5 5 0 10 0 3 4 1 0 15.0% 1450 M760 0 5 50 10 0 3 4 2 0 15.4% 1450 M761 0 5 5 0 10 0 3 4 3 0 15.7% 1450 M762 0 55 0 10 0 3 4 4 0 16.1% 1450 M763 0 5 5 0 10 0 4 0 0 0 11.7% 1450 M764 05 5 0 10 0 4 0 1 0 12.0% 1450 M765 0 5 5 0 10 0 4 0 2 0 12.4% 1450 M7660 5 5 0 10 0 4 0 3 0 12.7% 1450 M767 0 5 5 0 10 0 4 0 4 0 13.1% 1450M768 0 5 5 0 10 0 4 1 0 0 12.7% 1450 M769 0 5 5 0 10 0 4 1 1 0 13.0%1450 M770 0 5 5 0 10 0 4 1 2 0 13.4% 1450 M771 0 5 5 0 10 0 4 1 3 013.8% 1450 M772 0 5 5 0 10 0 4 1 4 0 14.1% 1450 M773 0 5 5 0 10 0 4 2 00 13.7% 1450 M774 0 5 5 0 10 0 4 2 1 0 14.0% 1450 M775 0 5 5 0 10 0 4 22 0 14.4% 1450 M776 0 5 5 0 10 0 4 2 3 0 14.8% 1450 M777 0 5 5 0 10 0 42 4 0 15.2% 1450 M778 0 5 5 0 10 0 4 3 0 0 14.7% 1450 M779 0 5 5 0 10 04 3 1 0 15.0% 1450 M780 0 5 5 0 10 0 4 3 2 0 15.4% 1450 M781 0 5 5 0 100 4 3 3 0 15.8% 1450 M782 0 5 5 0 10 0 4 3 4 0 16.2% 1450 M783 0 5 5 010 0 4 4 0 0 15.6% 1450 M784 0 5 5 0 10 0 4 4 1 0 16.0% 1450 M785 0 5 50 10 0 4 4 2 0 16.4% 1450 M786 0 5 5 0 10 0 4 4 3 0 16.8% 1450 M787 0 55 0 10 0 4 4 4 0 17.2% 1450 M788 0 5 7 0 10 0 0 0 1 0 8.9% 1500 M789 0 57 0 10 0 0 0 2 0 9.2% 1500 M790 0 5 7 0 10 0 0 0 3 0 9.6% 1500 M791 0 57 0 10 0 0 0 4 0 9.9% 1500 M792 0 5 7 0 10 0 0 1 0 0 9.6% 1500 M793 0 57 0 10 0 0 1 1 0 9.9% 1500 M794 0 5 7 0 10 0 0 1 2 0 10.3% 1500 M795 0 57 0 10 0 0 1 3 0 10.6% 1500 M796 0 5 7 0 10 0 0 1 4 0 11.0% 1500 M797 05 7 0 10 0 0 2 0 0 10.6% 1500 M798 0 5 7 0 10 0 0 2 1 0 10.9% 1500 M7990 5 7 0 10 0 0 2 2 0 11.3% 1500 M800 0 5 7 0 10 0 0 2 3 0 11.7% 1500M801 0 5 7 0 10 0 0 2 4 0 12.0% 1450 M802 0 5 7 0 10 0 0 3 0 0 11.6%1500 M803 0 5 7 0 10 0 0 3 1 0 12.0% 1500 M804 0 5 7 0 10 0 0 3 2 012.3% 1500 M805 0 5 7 0 10 0 0 3 3 0 12.7% 1500 M806 0 5 7 0 10 0 0 3 40 13.1% 1450 M807 0 5 7 0 10 0 0 4 0 0 12.6% 1500 M808 0 5 7 0 10 0 0 41 0 13.0% 1500 M809 0 5 7 0 10 0 0 4 2 0 13.3% 1500 M810 0 5 7 0 10 0 04 3 0 13.7% 1450 M811 0 5 7 0 10 0 0 4 4 0 14.1% 1450 M812 0 5 7 0 10 01 0 0 0 9.6% 1500 M813 0 5 7 0 10 0 1 0 1 0 10.0% 1500 M814 0 5 7 0 10 01 0 2 0 10.3% 1500 M815 0 5 7 0 10 0 1 0 3 0 10.7% 1450 M816 0 5 7 0 100 1 0 4 0 11.0% 1450 M817 0 5 7 0 10 0 1 1 0 0 10.6% 1500 M818 0 5 7 010 0 1 1 1 0 11.0% 1500 M819 0 5 7 0 10 0 1 1 2 0 11.4% 1450 M820 0 5 70 10 0 1 1 3 0 11.7% 1450 M821 0 5 7 0 10 0 1 1 4 0 12.1% 1450 M822 0 57 0 10 0 1 2 0 0 11.7% 1500 M823 0 5 7 0 10 0 1 2 1 0 12.0% 1500 M824 05 7 0 10 0 1 2 2 0 12.4% 1450 M825 0 5 7 0 10 0 1 2 3 0 12.7% 1450 M8260 5 7 0 10 0 1 2 4 0 13.1% 1450 M827 0 5 7 0 10 0 1 3 0 0 12.7% 1500M828 0 5 7 0 10 0 1 3 1 0 13.0% 1500 M829 0 5 7 0 10 0 1 3 2 0 13.4%1450 M830 0 5 7 0 10 0 1 3 3 0 13.8% 1450 M831 0 5 7 0 10 0 1 3 4 014.2% 1450 M832 0 5 7 0 10 0 1 4 0 0 13.7% 1500 M833 0 5 7 0 10 0 1 4 10 14.0% 1450 M834 0 5 7 0 10 0 1 4 2 0 14.4% 1450 M835 0 5 7 0 10 0 1 43 0 14.8% 1450 M836 0 5 7 0 10 0 1 4 4 0 15.2% 1450 M837 0 5 7 0 10 0 20 0 0 10.7% 1500 M838 0 5 7 0 10 0 2 0 1 0 11.1% 1450 M839 0 5 7 0 10 02 0 2 0 11.4% 1450 M840 0 5 7 0 10 0 2 0 3 0 11.8% 1450 M841 0 5 7 0 100 2 0 4 0 12.1% 1450 M842 0 5 7 0 10 0 2 1 0 0 11.7% 1450 M843 0 5 7 010 0 2 1 1 0 12.1% 1450 M844 0 5 7 0 10 0 2 1 2 0 12.4% 1450 M845 0 5 70 10 0 2 1 3 0 12.8% 1450 M846 0 5 7 0 10 0 2 1 4 0 13.2% 1450 M847 0 57 0 10 0 2 2 0 0 12.7% 1450 M848 0 5 7 0 10 0 2 2 1 0 13.1% 1450 M849 05 7 0 10 0 2 2 2 0 13.5% 1450 M850 0 5 7 0 10 0 2 2 3 0 13.8% 1450 M8510 5 7 0 10 0 2 2 4 0 14.2% 1450 M852 0 5 7 0 10 0 2 3 0 0 13.7% 1450M853 0 5 7 0 10 0 2 3 1 0 14.1% 1450 M854 0 5 7 0 10 0 2 3 2 0 14.5%1450 M855 0 5 7 0 10 0 2 3 3 0 14.9% 1450 M856 0 5 7 0 10 0 2 3 4 015.2% 1450 M857 0 5 7 0 10 0 2 4 0 0 14.7% 1450 M858 0 5 7 0 10 0 2 4 10 15.1% 1450 M859 0 5 7 0 10 0 2 4 2 0 15.5% 1450 M860 0 5 7 0 10 0 2 43 0 15.9% 1450 M861 0 5 7 0 10 0 2 4 4 0 16.3% 1450 M862 0 5 7 0 10 0 30 0 0 11.8% 1450 M863 0 5 7 0 10 0 3 0 1 0 12.1% 1450 M864 0 5 7 0 10 03 0 2 0 12.5% 1450 M865 0 5 7 0 10 0 3 0 3 0 12.9% 1450 M866 0 5 7 0 100 3 0 4 0 13.2% 1450 M867 0 5 7 0 10 0 3 1 0 0 12.8% 1450 M868 0 5 7 010 0 3 1 1 0 13.1% 1450 M869 0 5 7 0 10 0 3 1 2 0 13.5% 1450 M870 0 5 70 10 0 3 1 3 0 13.9% 1450 M871 0 5 7 0 10 0 3 1 4 0 14.3% 1450 M872 0 57 0 10 0 3 2 0 0 13.8% 1450 M873 0 5 7 0 10 0 3 2 1 0 14.2% 1450 M874 05 7 0 10 0 3 2 2 0 14.5% 1450 M875 0 5 7 0 10 0 3 2 3 0 14.9% 1450 M8760 5 7 0 10 0 3 2 4 0 15.3% 1450 M877 0 5 7 0 10 0 3 3 0 0 14.8% 1450M878 0 5 7 0 10 0 3 3 1 0 15.2% 1450 M879 0 5 7 0 10 0 3 3 2 0 15.6%1450 M880 0 5 7 0 10 0 3 3 3 0 15.9% 1450 M881 0 5 7 0 10 0 3 3 4 016.3% 1450 M882 0 5 7 0 10 0 3 4 0 0 15.8% 1450 M883 0 5 7 0 10 0 3 4 10 16.2% 1450 M884 0 5 7 0 10 0 3 4 2 0 16.6% 1450 M885 0 5 7 0 10 0 3 43 0 17.0% 1450 M886 0 5 7 0 10 0 3 4 4 0 17.4% 1450 M887 0 5 7 0 10 0 40 0 0 12.8% 1450 M888 0 5 7 0 10 0 4 0 1 0 13.2% 1450 M889 0 5 7 0 10 04 0 2 0 13.6% 1450 M890 0 5 7 0 10 0 4 0 3 0 14.0% 1450 M891 0 5 7 0 100 4 0 4 0 14.3% 1450 M892 0 5 7 0 10 0 4 1 0 0 13.8% 1450 M893 0 5 7 010 0 4 1 1 0 14.2% 1450 M894 0 5 7 0 10 0 4 1 2 0 14.6% 1450 M895 0 5 70 10 0 4 1 3 0 15.0% 1450 M896 0 5 7 0 10 0 4 1 4 0 15.4% 1450 M897 0 57 0 10 0 4 2 0 0 14.8% 1450 M898 0 5 7 0 10 0 4 2 1 0 15.2% 1450 M899 05 7 0 10 0 4 2 2 0 15.6% 1450 M900 0 5 7 0 10 0 4 2 3 0 16.0% 1450 M9010 5 7 0 10 0 4 2 4 0 16.4% 1450 M902 0 5 7 0 10 0 4 3 0 0 15.8% 1450M903 0 5 7 0 10 0 4 3 1 0 16.2% 1450 M904 0 5 7 0 10 0 4 3 2 0 16.6%1450 M905 0 5 7 0 10 0 4 3 3 0 17.0% 1400 M906 0 5 7 0 10 0 4 3 4 017.4% 1450 M907 0 5 7 0 10 0 4 4 0 0 16.8% 1450 M908 0 5 7 0 10 0 4 4 10 17.2% 1450 M909 0 5 7 0 10 0 4 4 2 0 17.6% 1450 M910 0 5 7 0 10 0 4 43 0 18.0% 1400 M911 0 5 7 0 10 0 4 4 4 0 18.4% 1450 M912 0 5 9 0 10 0 00 1 0 10.1% 1500 M913 0 5 9 0 10 0 0 0 2 0 10.4% 1450 M914 0 5 9 0 10 00 0 3 0 10.8% 1450 M915 0 5 9 0 10 0 0 0 4 0 11.2% 1450 M916 0 5 9 0 100 0 1 0 0 10.7% 1500 M917 0 5 9 0 10 0 0 1 1 0 11.1% 1500 M918 0 5 9 010 0 0 1 2 0 11.5% 1450 M919 0 5 9 0 10 0 0 1 3 0 11.8% 1450 M920 0 5 90 10 0 0 1 4 0 12.2% 1450 M921 0 5 9 0 10 0 0 2 0 0 11.8% 1500 M922 0 59 0 10 0 0 2 1 0 12.1% 1450 M923 0 5 9 0 10 0 0 2 2 0 12.5% 1450 M924 05 9 0 10 0 0 2 3 0 12.9% 1450 M925 0 5 9 0 10 0 0 2 4 0 13.2% 1450 M9260 5 9 0 10 0 0 3 0 0 12.8% 1500 M927 0 5 9 0 10 0 0 3 1 0 13.2% 1450M928 0 5 9 0 10 0 0 3 2 0 13.5% 1450 M929 0 5 9 0 10 0 0 3 3 0 13.9%1450 M930 0 5 9 0 10 0 0 3 4 0 14.3% 1450 M931 0 5 9 0 10 0 0 4 0 013.8% 1500 M932 0 5 9 0 10 0 0 4 1 0 14.2% 1450

In some embodiments, the alloy can possess a low FCC-BCC transitiontemperature. This criteria can be related to the likelihood of the alloyto retain an austenitic structure when deposited and thus be ‘readable’by certain measuring devices, as discussed further below. Readablecoatings can be non-magnetic and thus the thickness can be measured withstandard paint thickness gauges. This can be advantageous for manythermal spray applications.

Performance Criteria:

In some embodiments, the alloy can be described by performance criteria.The performance criteria that can be advantageous to the field ofthermal spray hardfacing is the hardness, wear resistance, coatingadhesion, and corrosion resistance.

In some embodiments, the Vickers hardness of the coating can be 400 orabove (or about 400 or above). In some embodiments, the Vickers hardnessof the coating can be 500 or above (or about 500 or above). In someembodiments, the Vickers hardness can be 550 or above (or about 550 orabove). In some embodiments, the Vickers hardness can be 600 or above(or about 600 or above). The specific microstructure disclosed hereincan allow for embodiments of the alloys to have high hardness.

In some embodiments, the adhesion strength of the coating can be 5,000psi or above (or about 5,000 psi or above). In some embodiments, theadhesion strength of the coating can be 7,500 psi or above (or about7,500 psi or above). In some embodiments, the adhesion strength of thecoating can be 10,000 psi or above (or about 10,000 psi or above).

In some embodiments, the abrasion resistance of the coating as measuredvia ASTM G65B testing can be 0.8 grams loss or below (or about 0.8 gramsloss or below). In some embodiments, the abrasion resistance of thecoating as measured via ASTM G65B testing can be 0.6 grams loss or below(or about 0.6 grams loss or below). In some embodiments, the abrasionresistance of the coating as measured via ASTM G65B testing can be 0.4grams loss or below (or about 0.4 grams loss or below).

In some embodiments, the adhesive wear resistance of the coating asmeasured via ASTM G77 testing, hereby incorporated by reference in itsentirety, can be 2 mm³ volume loss or below (or about 2 mm³ volume lossor below). In some embodiments, the adhesive wear resistance of thecoating as measured via ASTM G77 testing can be 0.5 mm³ volume loss orbelow (or about 0.5 mm³ volume loss or below). In some embodiments, theadhesive wear resistance of the coating as measured via ASTM G77 testingcan be 0.1 mm³ volume loss or below (or about 0.1 mm³ volume loss orbelow).

In some embodiments, the alloy can exhibit similar performance toconventional Cr-bearing thermal spray materials used for hardfacing. Themost exemplary and well used thermal spray hardfacing material possessesa chemical composition of Fe: BAL, Cr: 29, Si: 1, Mn: 2, B: 4, which isgenerally referred to in the industry as Armacor M. Armacor M possessesthe following properties which are relevant to thermal spray hardfacing:adhesion of about 8,000 psi, ASTM G65B mass loss of about 0.37 grams,ASTM G77 volume loss of about 0.07 mm³, and position in the galvanicseries in saltwater of about −500 mV. Armacor M is primarily made of Fe,Cr, and B, has a high melting temperature, and has no large atoms.

In some embodiments of this disclosure, the alloys can exhibit similarcoating adhesion and abrasive wear resistance as Armacor, where‘similar’ equates to within 25% (or within about 25%) of the measuredperformance properties of Armacor M or better. In some embodiments ofthis disclosure, the alloys can exhibit similar coating adhesion,abrasive wear resistance, and adhesive wear resistance as Armacor, where‘similar’ equates to within 25% (or within about 25%) of the measuredperformance properties of Armacor M or better. In some embodiments ofthis disclosure, the alloys can exhibit similar coating adhesion,abrasive wear resistance, adhesive wear resistance, and corrosionresistance as Armacor, where ‘similar’ equates to within 25% (or withinabout 25%) of the measured performance properties of Armacor M orbetter.

In some embodiments of this disclosure, the alloys can exhibit similarcoating adhesion and abrasive wear resistance as Armacor, where‘similar’ equates to within 10% (or within about 10%) of the measuredperformance properties of Armacor M or better. In some embodiments ofthis disclosure, the alloys can exhibit similar coating adhesion,abrasive wear resistance, and adhesive wear resistance as Armacor, where‘similar’ equates to within 10% (or within about 10%) of the measuredperformance properties of Armacor M or better. In some embodiments ofthis disclosure, the alloys can exhibit similar coating adhesion,abrasive wear resistance, adhesive wear resistance, and corrosionresistance as Armacor, where ‘similar’ equates to within 10% (or withinabout 10%) of the measured performance properties of Armacor M orbetter.

In some embodiments of this disclosure, the alloys can exhibit similarcoating adhesion and abrasive wear resistance as Armacor, where‘similar’ equates to within 1% (or within about 1%) of the measuredperformance properties of Armacor M or better. In some embodiments ofthis disclosure, the alloys can exhibit similar coating adhesion,abrasive wear resistance, and adhesive wear resistance as Armacor, where‘similar’ equates to within 1% (or within about 1%) of the measuredperformance properties of Armacor M or better. In some embodiments ofthis disclosure, the alloys can exhibit similar coating adhesion,abrasive wear resistance, adhesive wear resistance, and corrosionresistance as Armacor, where ‘similar’ equates to within 1% (or withinabout 1%) of the measured performance properties of Armacor M or better.

In some embodiments of this disclosure, the alloys can exhibit similarcoating adhesion and abrasive wear resistance as Armacor, where‘similar’ equates to within 0% (or within about 0%) of the measuredperformance properties of Armacor M or better. In some embodiments ofthis disclosure, the alloys can exhibit similar coating adhesion,abrasive wear resistance, and adhesive wear resistance as Armacor, where‘similar’ equates to within 0% (or within about 0%) of the measuredperformance properties of Armacor M or better. In some embodiments ofthis disclosure, the alloys can exhibit similar coating adhesion,abrasive wear resistance, adhesive wear resistance, and corrosionresistance as Armacor, where ‘similar’ equates to within 0% (or withinabout 0%) of the measured performance properties of Armacor M or better.

In some embodiments, the thermal spray coating can be ‘readable’. Areadable coating produces consistent thickness measurements with anElcometer™ thickness gauge, or similar device, when properly calibrated.Armacor M is not a readable alloy, unlike embodiments of the disclosure,as it is magnetic.

As a standard to verify ‘readability’, a 25 mil standard thermal spraycoupon is used for measurements. In some embodiments, the coatingthickness measurement can be accurate to within 5 mils (or within about5 mils) of the actual physical thickness. In some embodiments, thecoating thickness measurement can be accurate to within 3.5 mils (orwithin about 3.5 mils) of the actual physical thickness. In someembodiments, the coating thickness measurement can be accurate to within2 mils (or within about 2 mils) of the actual physical thickness.

In some embodiments, consistent measurements according to the abovecriteria, ±5 mils to actual physical thickness, can be made after thecoating has been exposed to heat for an extended period of time. Thiscan be advantageous because when the alloy is heated, there is apotential for a magnetic phase to precipitate out, which would make thealloy non-readable. This can be especially true for amorphous alloyswhich may be readable in amorphous form, but may crystallize in adifferent environment due to heat. Thus, in some embodiments, the alloycan remain non-magnetic even after being exposed to heat for asubstantial time period.

In some embodiments, the coating can be ‘readable’ after exposure to1100K (or about 1100K) for 2 hours (or about 2 hours) and cooled at arate of less than 10K/S (or less than about 10K/S). In some embodiments,the coating can be ‘readable’ after exposure to 1300K (or about 1300K)for 2 hours (or about 2 hours) and cooled at a rate of less than 10K/S(or less than 10K/S). In some embodiments, the coating can be ‘readable’after exposure to 1500K (or about 1500K) for 2 hours (or about 2 hours)and cooled at a rate of less than 10K/S (or less than about 10K/S). Itis expected that increased exposure times above 2 hours will notcontinue to affect the final ‘readability’ of these materials.

TABLE 3 List of alloy compositions and thermodynamic and kineticparameters which meet the criteria described in this disclosure,including the criteria pertained to coating non-magnetism andreadability. Large atom % is the total atom % of elements larger thaniron, Trans T is the FCC-BCC transition temperature and melt T is themelting temperature of the alloy. No. C Mn Mo Ni Si Large Atom % Trans TMelt T M934 0 19 20 0 10 30% 1000 1300 M935 0 20 19 0 10 31% 1000 1300M936 0 20 20 0 10 31% 900 1300 M937 0 13 11 4 5 20% 800 1500 M938 0 1311 5 5 20% 800 1500 M939 0 13 13 3 5 21% 800 1500 M940 0 13 13 4 5 21%800 1500 M941 0 13 13 5 5 21% 800 1500 M942 0 13 13 5 6 21% 850 1450M943 0 13 15 2 5 22% 800 1500 M944 0 13 15 3 5 22% 800 1500 M945 0 13 154 5 22% 800 1500 M946 0 13 15 4 6 22% 850 1450 M947 0 13 15 5 5 22% 8001500 M948 0 13 15 5 6 22% 850 1450 M949 0 16 7 1 6 20% 850 1500 M950 016 7 2 6 20% 850 1500 M951 0 16 7 3 6 20% 850 1500 M952 0 16 7 3 7 20%900 1500 M953 0 16 7 4 6 20% 800 1500 M954 0 16 7 4 7 20% 900 1500 M9550 16 7 5 6 20% 800 1500 M956 0 16 7 5 7 20% 900 1500 M957 0 16 9 1 6 21%850 1500 M958 0 16 9 2 6 21% 800 1500 M959 0 16 9 2 7 21% 900 1450 M9600 16 9 3 6 21% 800 1500 M961 0 16 9 3 7 21% 900 1450 M962 0 16 9 4 6 21%800 1500 M963 0 16 9 4 7 21% 900 1450 M964 0 16 9 4 8 21% 1000 1450 M9650 16 9 5 5 21% 750 1500 M966 0 16 9 5 6 21% 800 1500 M967 0 16 9 5 7 21%850 1450 M968 0 16 9 5 8 21% 1000 1450 M969 0 16 11 0 5 23% 800 1500M970 0 16 11 1 5 23% 800 1500 M971 0 16 11 1 6 22% 850 1500 M972 0 16 111 7 22% 900 1450 M973 0 16 11 2 5 23% 750 1500 M974 0 16 11 2 6 22% 8001500 M975 0 16 11 2 7 22% 900 1450 M976 0 16 11 3 5 23% 750 1500 M977 016 11 3 6 22% 800 1500 M978 0 16 11 3 7 22% 850 1450 M979 0 16 11 3 822% 1000 1400 M980 0 16 11 4 5 23% 750 1500 M981 0 16 11 4 6 22% 8001500 M982 0 16 11 4 7 22% 850 1450 M983 0 16 11 4 8 22% 950 1400 M984 016 11 5 5 23% 750 1500 M985 0 16 11 5 6 22% 800 1500 M986 0 16 11 5 722% 850 1450 M987 0 16 13 0 5 24% 800 1500 M988 0 16 13 1 5 24% 750 1500M989 0 16 13 1 6 24% 800 1450 M990 0 16 13 1 7 23% 900 1450 M991 0 16 132 5 24% 750 1500 M992 0 16 13 2 6 24% 800 1450 M993 0 16 13 2 7 23% 8501450 M994 0 16 13 2 8 23% 950 1400 M995 0 16 13 3 5 24% 750 1500 M996 016 13 3 6 24% 800 1450 M997 0 16 13 3 7 23% 850 1450 M998 0 16 13 4 524% 750 1500 M999 0 16 13 4 6 24% 750 1450 M1000 0 16 13 5 5 24% 7501500 M1001 0 16 15 0 5 25% 750 1450 M1002 0 16 15 0 6 25% 800 1450 M10030 16 15 0 7 25% 900 1400 M1004 0 16 15 1 5 25% 750 1450 M1005 0 16 15 16 25% 800 1450 M1006 0 16 15 1 7 25% 850 1400 M1007 0 16 15 2 5 25% 7501450 M1008 0 16 15 2 6 25% 750 1450 M1009 0 16 15 3 5 25% 750 1450 M10100 16 15 3 6 25% 750 1450 M1011 0 16 15 4 5 25% 750 1450 M1012 0 19 7 0 623% 800 1500 M1013 0 19 7 0 7 22% 900 1450 M1014 0 19 7 1 6 23% 800 1500M1015 0 19 7 1 7 22% 900 1450 M1016 0 19 7 2 6 23% 750 1500 M1017 0 19 72 7 22% 850 1450 M1018 0 19 7 2 8 22% 1000 1450 M1019 0 19 7 3 6 23% 7501500 M1020 0 19 7 3 7 22% 850 1450 M1021 0 19 7 3 8 22% 950 1450 M1022 019 7 4 6 23% 750 1500 M1023 0 19 7 4 7 22% 850 1450 M1024 0 19 7 4 8 22%950 1450 M1025 0 19 7 5 5 23% 750 1500 M1026 0 19 7 5 6 23% 750 1500M1027 0 19 7 5 7 22% 800 1450 M1028 0 19 7 5 8 22% 950 1450 M1029 0 19 90 5 24% 750 1500 M1030 0 19 9 0 6 24% 800 1500 M1031 0 19 9 0 7 24% 9001450 M1032 0 19 9 1 5 24% 750 1500 M1033 0 19 9 1 6 24% 750 1500 M1034 019 9 1 7 24% 850 1450 M1035 0 19 9 1 8 24% 1000 1400 M1036 0 19 9 2 524% 750 1500 M1037 0 19 9 2 6 24% 750 1500 M1038 0 19 9 2 7 24% 800 1450M1039 0 19 9 2 8 24% 950 1400 M1040 0 19 9 3 5 24% 700 1500 M1041 0 19 93 6 24% 750 1500 M1042 0 19 9 3 7 24% 800 1450 M1043 0 19 9 3 8 24% 9001400 M1044 0 19 9 4 5 24% 700 1500 M1045 0 19 9 4 6 24% 750 1500 M1046 019 9 4 7 24% 800 1450 M1047 0 19 9 5 5 24% 700 1500 M1048 0 19 9 5 6 24%750 1500 M1049 0 19 11 0 5 26% 700 1500 M1050 0 19 11 0 6 25% 750 1450M1051 0 19 11 0 7 25% 850 1450 M1052 0 19 11 0 8 25% 1000 1400 M1053 019 11 1 5 26% 700 1500 M1054 0 19 11 1 6 25% 750 1450 M1055 0 19 11 1 725% 800 1450 M1056 0 19 11 1 8 25% 950 1400 M1057 0 19 11 2 5 26% 7001500 M1058 0 19 11 2 6 25% 750 1450 M1059 0 19 11 2 7 25% 800 1450 M10600 19 11 3 5 26% 700 1500 M1061 0 19 11 3 6 25% 750 1450 M1062 0 19 11 37 25% 800 1450 M1063 0 19 11 4 5 26% 700 1500 M1064 0 19 11 4 6 25% 7501450 M1065 0 19 11 5 5 26% 700 1500 M1066 0 19 13 0 5 27% 700 1500 M10670 19 13 0 6 27% 750 1450 M1068 0 19 13 0 7 26% 800 1400 M1069 0 19 13 15 27% 700 1450 M1070 0 19 13 1 6 27% 750 1450 M1071 0 19 13 2 5 27% 7001450 M1072 0 19 13 3 5 27% 700 1450 M1073 0 19 15 0 5 28% 700 1450 M10740 19 15 0 6 28% 750 1400 M1075 0 19 15 1 5 28% 700 1450 M1076 0 22 7 0 526% 700 1500 M1077 0 22 7 0 6 26% 750 1500 M1078 0 22 7 0 7 25% 850 1450M1079 0 22 7 0 8 25% 1000 1400 M1080 0 22 7 1 5 26% 700 1500 M1081 0 227 1 6 26% 700 1500 M1082 0 22 7 1 7 25% 800 1450 M1083 0 22 7 1 8 25%950 1400 M1084 0 22 7 2 5 26% 700 1500 M1085 0 22 7 2 6 26% 700 1500M1086 0 22 7 2 7 25% 800 1450 M1087 0 22 7 2 8 25% 900 1400 M1088 0 22 73 5 26% 700 1500 M1089 0 22 7 3 6 26% 700 1500 M1090 0 22 7 3 7 25% 7501450 M1091 0 22 7 4 5 26% 700 1500 M1092 0 22 7 4 6 26% 700 1500 M1093 022 7 5 5 26% 700 1500 M1094 0 22 9 0 5 27% 700 1500 M1095 0 22 9 0 6 27%700 1450 M1096 0 22 9 0 7 27% 800 1450 M1097 0 22 9 0 8 26% 950 1400M1098 0 22 9 1 5 27% 700 1500 M1099 0 22 9 1 6 27% 700 1450 M1100 0 22 91 7 27% 750 1450 M1101 0 22 9 2 5 27% 700 1500 M1102 0 22 9 2 6 27% 7001450 M1103 0 22 9 3 5 27% 700 1500 M1104 0 22 9 3 6 27% 700 1450 M1105 022 9 4 5 27% 700 1500 M1106 0 22 11 0 5 29% 700 1500 M1107 0 22 11 0 628% 700 1450 M1108 0 22 11 1 5 29% 650 1500 M1109 0 22 13 0 5 30% 6501450 M1110 0 25 7 0 5 29% 650 1500 M1111 0 25 7 0 6 29% 700 1450 M1112 025 7 0 7 28% 750 1450 M1113 0 25 7 1 5 29% 650 1500 M1114 0 25 7 1 6 29%650 1450 M1115 0 25 7 2 5 29% 650 1500 M1116 0 25 7 3 5 29% 650 1500M1117 0 25 9 0 5 30% 650 1500 M1118 0 25 9 0 6 30% 650 1450 M1119 0 25 91 5 30% 650 1500 M1120 0.25 16 7 3 5 20% 750 1500 M1121 0.25 16 7 4 520% 750 1500 M1122 0.25 16 7 5 5 20% 750 1500 M1123 0.25 16 9 0 5 21%800 1500 M1124 0.25 19 7 0 5 23% 750 1500 M1125 0.25 19 7 1 5 23% 7501500 M1126 0.25 19 7 2 5 23% 750 1500 M1127 0.25 19 7 3 5 23% 750 1500M1128 0.25 19 7 4 5 23% 700 1500 M1129 0.25 19 7 5 5 23% 700 1500 M11300.25 19 9 0 5 24% 750 1500 M1131 0.25 22 7 0 5 26% 700 1500 M1132 0.2522 7 1 5 26% 700 1500 M1133 0.25 22 7 2 5 26% 700 1500 M1134 0.25 22 7 35 26% 700 1500 M1135 0.25 22 7 4 5 26% 700 1500 M1136 0.25 22 7 5 5 26%700 1500 M1137 0.25 22 9 0 5 27% 700 1500 M1138 0.25 25 7 0 5 29% 6501500 M1139 0.25 25 7 1 5 29% 650 1500 M1140 0.25 25 7 2 5 29% 650 1500M1141 0.25 25 9 0 5 30% 650 1500

Applications and Processes for Use:

Embodiments of alloys disclosed herein can be used in a variety ofapplications and industries. Some non-limiting examples of applicationsof use include:

Surface mining applications including but not limited to the followingcomponents and coatings for the following components: wear resistantsleeves and/or wear resistant hardfacing for slurry pipelines, mud pumpcomponents including pump housing or impeller or hardfacing for mud pumpcomponents, ore feed chute components including chute blocks orhardfacing of chute blocks, separation screens including but not limitedto rotary breaker screens, banana screens, and shaker screens, linersfor autogenous grinding mills and semi-autogenous grinding mills, groundengaging tools and hardfacing for ground engaging tools, wear plate forbuckets and dumptruck liners, heel blocks and hardfacing for heel blockson mining shovels, grader blades and hardfacing for grader blades,stacker reclaimers, siazer crushers, general wear packages for miningcomponents and other communition components.

Upstream oil and gas applications including but not limited to thefollowing components and coatings for the following components: Downholecasing and downhole casing, drill pipe and coatings for drill pipeincluding hardbanding, mud management components, mud motors, frackingpump sleeves, fracking impellers, fracking blender pumps, stop collars,drill bits and drill bit components, directional drilling equipment andcoatings for directional drilling equipment including stabilizers andcentralizers, blow out preventers and coatings for blow out preventersand blow out preventer components including the shear rams, oil countrytubular goods and coatings for oil country tubular goods.

Downstream oil and gas applications including but not limited to thefollowing components and coatings for the following components: Processvessels and coating for process vessels including steam generationequipment, amine vessels, distillation towers, cyclones, catalyticcrackers, general refinery piping, corrosion under insulationprotection, sulfur recovery units, convection hoods, sour stripperlines, scrubbers, hydrocarbon drums, and other refinery equipment andvessels.

Pulp and paper applications including but not limited to the followingcomponents and coatings for the following components: Rolls used inpaper machines including yankee dryers and other dryers, calendar rolls,machine rolls, press rolls, digesters, pulp mixers, pulpers, pumps,boilers, shredders, tissue machines, roll and bale handling machines,doctor blades, evaporators, pulp mills, head boxes, wire parts, pressparts, M.G. cylinders, pope reels, winders, vacuum pumps, deflakers, andother pulp and paper equipment.

Power generation applications including but not limited to the followingcomponents and coatings for the following components: boiler tubes,precipitators, fireboxes, turbines, generators, cooling towers,condensers, chutes and troughs, augers, bag houses, ducts, ID fans, coalpiping, and other power generation components.

Agriculture applications including but not limited to the followingcomponents and coatings for the following components: chutes, basecutter blades, troughs, primary fan blades, secondary fan blades, augersand other agricultural applications.

Construction applications including but not limited to the followingcomponents and coatings for the following components: cement chutes,cement piping, bag houses, mixing equipment and other constructionapplications.

Machine element applications including but not limited to the followingcomponents and coatings for the following components: Shaft journals,paper rolls, gear boxes, drive rollers, impellers, general reclamationand dimensional restoration applications and other machine elementapplications.

Steel applications including but not limited to the following componentsand coatings for the following components: cold rolling mills, hotrolling mills, wire rod mills, galvanizing lines, continue picklinglines, continuous casting rolls and other steel mill rolls, and othersteel applications.

Embodiments of alloys disclosed herein can be produced and or depositedin a variety of techniques effectively. Some non-limiting examples ofprocesses include:

Thermal spray process including but not limited to those using a wirefeedstock such as twin wire arc, spray, high velocity arc spray,combustion spray and those using a powder feedstock such as highvelocity oxygen fuel, high velocity air spray, plasma spray, detonationgun spray, and cold spray. Wire feedstock can be in the form of a metalcore wire, solid wire, or flux core wire. Powder feedstock can be eithera single homogenous alloy or a combination of multiple alloy powderwhich result in the desired chemistry when melted together.

Welding processes including but not limited to those using a wirefeedstock including but not limited to metal inert gas (MIG) welding,tungsten inert gas (TIG) welding, arc welding, submerged arc welding,open arc welding, bulk welding, laser cladding, and those using a powderfeedstock including but not limited to laser cladding and plasmatransferred arc welding. Wire feedstock can be in the form of a metalcore wire, solid wire, or flux core wire. Powder feedstock can be eithera single homogenous alloy or a combination of multiple alloy powderwhich result in the desired chemistry when melted together.

Casting processes including but not limited to processes typical toproducing cast iron including but not limited to sand casting, permanentmold casting, chill casting, investment casting, lost foam casting, diecasting, centrifugal casting, glass casting, slip casting and processtypical to producing wrought steel products including continuous castingprocesses.

Post processing techniques including but not limited to but not limitedto rolling, forging, surface treatments such as carburizing, nitriding,carbonitriding, heat treatments including but not limited toaustenitizing, normalizing, annealing, stress relieving, tempering,aging, quenching, cryogenic treatments, flame hardening, inductionhardening, differential hardening, case hardening, decarburization,machining, grinding, cold working, work hardening, and welding.

One of the more applicable uses of this technology is in applicationswhere coatings are deposited on-site, in the field, or in locationswhere proper ventilation, dust collection, and other safety measurescannot be easily met. Some well-known non-limiting examples of theseapplications include power generation applications such as the coatingof boiler tubes, upstream refinery applications such as the coating ofrefinery vessels, and pulp and paper applications such as the coatingand grinding of yankee dryers.

EXAMPLES

The following examples are intended to be illustrative and non-limiting.

Example 1

The previously disclosed alloy #4, Fe: BAL, Mn: about 5, Mo: about 13,Si: about 10 was produced in the form of a 40 gram trial ingot to verifyhardness and thermal spray vitrification potential. The ingot hardnesswas measured to be 534 Vickers (converting from a Rockwell Cmeasurement). The microstructure of the ingot showed a fully eutecticstructure indicating a strong possibility for amorphous ornanocrystalline structure under the rapid cooling rate of the sprayprocess. This material has been selected for manufacture into 1/16″cored thermal spray wire for twin wire arc spray trials after slightmodification to the alloy #14, Fe: BAL, Mn: about 5, Mo: about 13, Si:about 10, Al: about 2.

Example 2

The previously presented alloy #5, Fe: BAL, Mn: about 5, Mo: about 7,Si: about 10 was produced in the form of a 40 gram trial ingot to verifyhardness and thermal spray vitrification potential. The ingot hardnesswas measured to be 534 Vickers (converting from a Rockwell Cmeasurement). The microstructure of the ingot showed a fully eutecticstructure indicating a strong possibility for amorphous ornanocrystalline structure under the rapid cooling rate of the sprayprocess. This material has been selected for manufacture into 1/16″cored thermal spray wire for twin wire arc spray trials after slightmodification to alloy #15, Fe: BAL, Mn: about 5, Mo: about 7, Si: about10, Al: about 2.

Example 3

The previously disclosed alloy #8, Fe: BAL, C: about 0.25, Mn: about 19,Mo: about 7, Si: about 5 was produced in the form of a 40 gram ingot toverify hardness, thermal spray vetrification potential and magneticpermeability. In this example, the alloy candidate is being developed asa ‘readable’ coating which requires the alloy to be non-magnetic in thesprayed form. The ingot hardness was measured to be 300 Vickers(converting from a Rockwell C measurement). While this is below thedesired hardness threshold, it is well known by those skilled in the artthat the rapid cooling process achieved in thermal spray will increasethe hardness of the alloy in this form. Thus, it is not unreasonable toexpect an increase in hardness in the sprayed form up to the desiredlevel of 400 Vickers. The relative magnetic permeability was measuredvia a Low-Mu Magnetic Permeability Tester and was determined to be lessthan 1.01, well below the threshold required to ensure ‘readability’.

Example 4

The previously disclosed alloy #5, Fe: BAL, Mn: about 5, Mo: about 7,Si: about 10 was produced in the form of a cored thermal spray wire.This alloy was sprayed using the twin wire arc spray technique,specifically using the parameters shown in

Table 3. A series of tests were run to evaluate the alloys performancein reference to standard Cr-bearing thermal spray materials used forhardfacing. The specific alloy of reference is known by the commercialnames, Armacor M, TAFA 95MXC, PMet 273, etc. and has an alloycomposition of about Fe: BAL, Cr: 29, Si: 1, Mn: 2, B: 4. Table 2highlights the result of the testing. As shown in Table 4, Alloy #5 hascomparable adhesion and abrasion resistance as measure via ASTM G65Btesting.

TABLE 2 List of properties of disclosed alloys in relation to Armacor MAlloy Adhesion ASTM G65B ASTM G77 Armacor M 8,000 ± 500 psi 0.37 0.07Alloy #4 8,000 ± 500 psi 0.37 0.07 Alloy #5 8,000 ± 500 psi 0.46 1.55

TABLE 3 Spray parameters used in Example 4 and 5 testing Air pressure 60psi Voltage 38 V Amperage 125 A

Example 5

The previously disclosed alloy #4, Fe: BAL, Mn: about 5, Mo: about 7,Si: about 10 was produced in the form of a cored thermal spray wire.This alloy was sprayed using the twin wire arc spray technique using theparameters shown in

Table 3. Yankee dryers are typically sprayed using this parameter set. Aseries of tests were run to evaluate the alloys performance in referenceto standard Cr-bearing thermal spray materials used for hardfacingsimilar to that described in Example 4. The preliminary results of thistesting are shown in Table 2.

As shown, Alloy #4 replicates the key performance criteria of Armacor Min all key criteria. As Alloy #4 represents an exemplary embodiment ofthis disclosure, additional testing was performed in order to compareother performance criteria specifically as it relates to the coating ofyankee dryers, a specific article of manufacture used in paper machines.This testing including corrosion testing, grinding studies, spraycharacteristics, thorough metallographic evaluation, and evaluation ofsurface properties as related to surface tension. In all cases, alloy #4was deemed to have similar or better performance than the Armacor Mcoating.

Corrosion testing was conducted by exposing the coating to saltwater andmeasuring the voltage against a reference bare steel plate, which couldbe then used to place the material on the Galvanic Series. Both theArmacor M and Alloy #4 coatings showed significant rust on the coatingsurface after the 2 week test exposure. The position of the Armacor Mcoating on the galvanic series is −450 to −567 and the position of Alloy#4 is −510 to −640. Increasingly negative values reflect more activepotentials, which is less desirable as it indicates reduced corrosionresistance. This represents a ‘similarity’ in that the quantifiedperformance does not vary by more than 25%.

Grinding studies were performed due to its specific relevance to theyankee dryer application. In this application it is desirable for thecoating to exhibit faster grinding times, as it reduces the downtime ofthe paper machine. Grinding times were quantified by removing a specificmaterial thickness and measuring the tie to do so, as shown in

Table 4. As shown, Alloy #4 showed reduced grinding time, which isadvantageous.

TABLE 4 Grinding Study Measurements Thickness Time to Grind (sec)Removed Alloy #4 ARM-M % Change  5 mil 140 s 150 s  7.14% 10 mil 210 s210 s    0% 15 mil 310 s 345 s 11.29% 20 mil 398 s 488 s 22.61%

The characteristics of the spray for both materials was also studied. Itwas evident that Alloy #4 produced significantly less dust duringspraying than Armacor M, which is desirable. Metallographic examinationalso showed that less oxides were present in the Alloy #4 coating, 7%versus 13% in the Armacor M coating.

Finally the surface tension properties of each coating were evaluated.In the Yankee dryer application it is desirable for the coating to behydrophilic, which enables the adsorption of water based organiccompounds used in paper making into the surface. The contact angle thata water droplet makes on the surface can be used to quantify the surfacetension of the material. The Armacor M water droplet formed a 63.9°angle, and Alloy #4 formed a 41.5° angle. A smaller angle indicatesincreased hydrophillicity, which is advantageous because in Yankee dryerapplications, a monoammonium phosphate (MAP) water-based solution istypically sprayed onto the coating for paper release properties. It canbe advantageous for this water-based solution to immerse itself into thecoating structure and stick well to the coating surface, which can beenhanced by having a hydrophilic coating.

From the foregoing description, it will be appreciated that an inventivechromium free hardfacing alloy and method of manufacturing aredisclosed. While several components, techniques and aspects have beendescribed with a certain degree of particularity, it is manifest thatmany changes can be made in the specific designs, constructions andmethodology herein above described without departing from the spirit andscope of this disclosure.

Certain features that are described in this disclosure in the context ofseparate implementations can also be implemented in combination in asingle implementation. Conversely, various features that are describedin the context of a single implementation can also be implemented inmultiple implementations separately or in any suitable subcombination.Moreover, although features may be described above as acting in certaincombinations, one or more features from a claimed combination can, insome cases, be excised from the combination, and the combination may beclaimed as any subcombination or variation of any subcombination.

Moreover, while methods may be depicted in the drawings or described inthe specification in a particular order, such methods need not beperformed in the particular order shown or in sequential order, and thatall methods need not be performed, to achieve desirable results. Othermethods that are not depicted or described can be incorporated in theexample methods and processes. For example, one or more additionalmethods can be performed before, after, simultaneously, or between anyof the described methods. Further, the methods may be rearranged orreordered in other implementations. Also, the separation of varioussystem components in the implementations described above should not beunderstood as requiring such separation in all implementations, and itshould be understood that the described components and systems cangenerally be integrated together in a single product or packaged intomultiple products. Additionally, other implementations are within thescope of this disclosure.

Conditional language, such as “can,” “could,” “might,” or “may,” unlessspecifically stated otherwise, or otherwise understood within thecontext as used, is generally intended to convey that certainembodiments include or do not include, certain features, elements,and/or steps. Thus, such conditional language is not generally intendedto imply that features, elements, and/or steps are in any way requiredfor one or more embodiments.

Conjunctive language such as the phrase “at least one of X, Y, and Z,”unless specifically stated otherwise, is otherwise understood with thecontext as used in general to convey that an item, term, etc. may beeither X, Y, or Z. Thus, such conjunctive language is not generallyintended to imply that certain embodiments require the presence of atleast one of X, at least one of Y, and at least one of Z.

Language of degree used herein, such as the terms “approximately,”“about,” “generally,” and “substantially” as used herein represent avalue, amount, or characteristic close to the stated value, amount, orcharacteristic that still performs a desired function or achieves adesired result. For example, the terms “approximately”, “about”,“generally,” and “substantially” may refer to an amount that is withinless than or equal to 10% of, within less than or equal to 5% of, withinless than or equal to 1% of, within less than or equal to 0.1% of, andwithin less than or equal to 0.01% of the stated amount. If the statedamount is 0 (e.g., none, having no), the above recited ranges can bespecific ranges, and not within a particular % of the value. Forexample, within less than or equal to 10 wt./vol. % of, within less thanor equal to 5 wt./vol. % of, within less than or equal to 1 wt./vol. %of, within less than or equal to 0.1 wt./vol. % of, and within less thanor equal to 0.01 wt./vol. % of the stated amount.

Some embodiments have been described in connection with the accompanyingdrawings. The figures are drawn to scale, but such scale should not belimiting, since dimensions and proportions other than what are shown arecontemplated and are within the scope of the disclosed inventions.Distances, angles, etc. are merely illustrative and do not necessarilybear an exact relationship to actual dimensions and layout of thedevices illustrated. Components can be added, removed, and/orrearranged. Further, the disclosure herein of any particular feature,aspect, method, property, characteristic, quality, attribute, element,or the like in connection with various embodiments can be used in allother embodiments set forth herein. Additionally, it will be recognizedthat any methods described herein may be practiced using any devicesuitable for performing the recited steps.

While a number of embodiments and variations thereof have been describedin detail, other modifications and methods of using the same will beapparent to those of skill in the art. Accordingly, it should beunderstood that various applications, modifications, materials, andsubstitutions can be made of equivalents without departing from theunique and inventive disclosure herein or the scope of the claims.

What is claimed is:
 1. A work piece having at least one surface, thework piece comprising: a coating applied to the at least one surface,the coating comprising an Fe-based alloy having substantially nochromium, having substantially no carbides, and having substantially noborides; wherein the alloy comprises a Vickers hardness of at least 500and an adhesion strength of at least 5,000 psi.
 2. The work piece ofclaim 1, wherein the coating comprises Fe and, in weight percent: B:about 0-4; C: about 0-0.25; Si: about 0-15; Mn: about 0 to 25; Mo: about0-29; Nb: about 0-2; Ta: about 0-4; Ti: about 0-4; V: about 0-10; W:about 0-6; Zr: about 0-10; wherein B+C+Si is about 4-15; and wherein(Mo+Mn+Nb+Ta+Ti+V+W+Zr) is about 5 to
 38. 3. The work piece of claim 1,wherein the coating comprises Fe and in weight percent: C: about 0 to0.25; Mn: about 5 to 19; Mo: about 7 to 23; Ni: about 0 to 4; and Si:about 5 to
 10. 4. The work piece of claim 1, wherein the coatingcomprises one or more of the following compositions in weight percent:Fe, Mn: about 5, Mo: about 13, Si: about 10, Al: about 2; or Fe, Mn:about 5, Mo: about 7, Si: about 10, Al: about
 2. 5. The work piece ofclaim 1, wherein the coating is non-magnetic and the coating thicknesscan be accurately measured with an Elcometer™ thickness gauge or similardevice after it has been exposed to temperatures exceeding about 1100 Kfor 2 hours or more and then slow cooled at a rate of 10K/s or less. 6.The work piece of claim 1, wherein the coating is amorphous.
 7. The workpiece of claim 1, wherein the coating is nanocrystalline, as defined byhaving a grain size of 100 nm or less.
 8. The work piece of claim 1,wherein the coating is applied via a thermal spray process.
 9. The workpiece of claim 1, wherein the coating is applied via a twin wire arcspray process.
 10. The work piece of claim 1, wherein the work piece isa yankee dryer.
 11. The work piece of claim 1, wherein the work piece isa roller used in a paper making machine.
 12. An article of manufacturecomprising: an Fe-based coating having substantially no chromium;wherein the coating possesses a melting temperature of 1500K or below;wherein the coating possesses a large atom concentration of at least 5atom %, large atoms being of the group consisting of Mn, Mo, Nb, Ta, Ti,V, W, and Zr; and wherein the coating is a primarily single phasefine-grained structure of either martensite, ferrite, or austenite. 13.The article of manufacture of claim 12, wherein the coating comprises,in weight percent: B: about 0-4; C: about 0-0.25; Si: about 0-15; Mn:about 0 to 25; Mo: about 0-29; Nb: about 0-2; Ta: about 0-4; Ti: about0-4; V: about 0-10; W: about 0-6; Zr: about 0-10; wherein B+C+Si isabout 4-15; and wherein (Mo+Mn+Nb+Ta+Ti+V+W+Zr) is about 5 to
 38. 14.The article of manufacture of claim 12, wherein the coating comprises Feand in weight percent: C: about 0 to 0.25; Mn: about 5 to 19; Mo: about7 to 23; Ni: about 0 to 4; and Si: about 5 to
 10. 15. The work piece ofclaim 12, wherein the coating comprises one or more of the followingcompositions in weight percent: Fe, Mn: about 5, Mo: about 13, Si: about10, Al: about 2; or Fe, Mn: about 5, Mo: about 7, Si: about 10, Al:about
 2. 16. The article of manufacture of claim 12, wherein the coatingis non-magnetic and the coating thickness can be accurately measuredwith an Elcometer™ thickness gauge or similar device after it has beenexposed to temperatures exceeding about 1100 K for 2 hours or more andthen slow cooled at a rate of 10K/s or less.
 17. The article ofmanufacture of claim 12, wherein the coating comprises a Vickershardness of at least 500 and an adhesion strength of at least 5,000 psi.18. The article of manufacture of claim 12, wherein the coating isapplied via the twin wire arc spray process.
 19. The article ofmanufacture of claim 12, wherein the coating is amorphous.
 20. Thearticle of manufacture of claim 12, wherein the coating isnanocrystalline, as defined by having a grain size of 100 nm or less.21. The article of manufacture of claim 12, wherein the coating isapplied via a thermal spray process.
 22. The article of manufacture ofclaim 12, wherein the coating is applied onto a roller used in a papermaking machine.
 23. The article of manufacture of claim 12, wherein thecoating is applied onto a Yankee Dryer.
 24. The article of manufactureof claim 12, wherein the coating is applied onto a boiler tube.
 25. Awork piece having at least one surface, the work piece comprising: acoating applied to the at least one surface, the coating comprising anFe-based alloy having less than 1 wt. % chromium, less than 5 vol. %carbides, and less than 5 vol. % borides; wherein the alloy comprises aVickers hardness of at least 500 and an adhesion strength of at least5,000 psi.
 26. The work piece of claim 25, wherein the alloy has lessthan 1 vol. % carbides and less than 1 vol. % borides.